Wiley, Journal of Polymer Science Part B: Polymer Physics, 16(37), p. 2229-2238, 1999
DOI: 10.1002/(sici)1099-0488(19990815)37:16<2229::aid-polb25>3.0.co;2-c
Wiley, Journal of Polymer Science Part B: Polymer Physics, 16(37), p. 2229-2238
DOI: 10.1002/(sici)1099-0488(19990815)37:16<2229::aid-polb25>3.3.co;2-3
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The phase behavior of intermediately segregated (χN = 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 fPE = 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 〈fPE〉 = 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. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2229–2238, 1999