Despite its wide occurrence in soft confined block co-polymers, breakout crystallization remains poorly understood and is difficult to control. In this work, thin films of cylinder-forming poly(butadiene)-block-poly(ε-caprolactone) (PB-b-PCL) diblock co-polymers, with PCL being the minority block, have been chosen as the study subject. We demonstrate a new route to study the breakout crystallization by obtaining the microphase separation structure within terraced lamellae first and then in situ tracking down the lamellar coalescence, resulting from the development of the crystal growth front. We find that the crystal growth front has sucked materials from the surrounding amorphous lamellae, which lead to the decrease of the lamellar zones and coalescence of the microphase separation structure. Dividing the breakout crystallization into parallel breakout and vertical breakout, we illustrate that it is the crystallization-driven molecular diffusion that make the molecules overcome the topography constraint and grow into large-scale spherulite. Moreover, the results show that the polymer microphase separation structure has a significant influence on the crystal nucleation and greatly retarded the crystal growth rate. With a well-designed microphase separation structure within terraces and an easily tunable atomic force microscopy in situ imaging technique, an intensive study of the breakout crystallization and concomitant microdomain coalescence has been offered.
© 2012 American Chemical Society