Thermal processing of diblock copolymer melts mimics metallurgy

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Science  05 May 2017:
Vol. 356, Issue 6337, pp. 520-523
DOI: 10.1126/science.aam7212

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When polymers behave like metals

Diblock copolymers, in which two dissimilar chains are chemically linked, can show a rich array of morphologies. These are usually attained by slow cooling to give the chains time to find their thermodynamically preferred arrangements. Rather than using slow cooling, Kim et al. rapidly quenched their materials from the disordered state and then annealed at low to moderate temperatures (see the Perspective by Stein). Different processing routes drove assembly into a variety of low-dimensional phases more typical of metal alloys.

Science, this issue p. 520; see also p. 487


Small-angle x-ray scattering experiments conducted with compositionally asymmetric low molar mass poly(isoprene)-b-poly(lactide) diblock copolymers reveal an extraordinary thermal history dependence. The development of distinct periodic crystalline or aperiodic quasicrystalline states depends on how specimens are cooled from the disordered state to temperatures below the order-disorder transition temperature. Whereas direct cooling leads to the formation of documented morphologies, rapidly quenched samples that are then heated from low temperature form the hexagonal C14 and cubic C15 Laves phases commonly found in metal alloys. Self-consistent mean-field theory calculations show that these, and other associated Frank-Kasper phases, have nearly degenerate free energies, suggesting that processing history drives the material into long-lived metastable states defined by self-assembled particles with discrete populations of volumes and polyhedral shapes.

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