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arXiv · 1406.1783

Effect of chain stiffness on the competition between crystallization and glass-formation in model colloidal polymers

Hong T. Nguyen·Tyler B. Smith·Robert S. Hoy·Nikos Ch. Karayiannis
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Abstract

We map out the solid-state morphologies formed by model soft-pearl-necklace polymers as a function of bending stiffness $k_b$ spanning the range from fully flexible to rodlike chains. The ratio of Kuhn length to bead diameter ($l_K/r_0$) increases monotonically with increasing $k_b$ and yields a one-parameter model that relates chain shape to bulk morphology and yields insights into the packing of anisotropic particles. In the flexible limit, monomers occupy the sites of close-packed crystallites while chains retain random-walk-like order. In the rodlike limit, nematic chain ordering typical of lamellar precursors coexists with close-packing. At intermediate values of bending stiffness the competition between random-walk-like and nematic chain ordering produces glass-formation; the range of $k_b$ over which this occurs increases with the thermal cooling rate $|\dot{T}|$ implemented in our molecular dynamics simulations. Finally, values of $k_b$ between the glass-forming and rodlike ranges produce complex ordered phases such as close-packed spirals. Our results should prove useful for rational design of dense colloidal-polymer phases with desired morphologies.

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Hong T. Nguyen, Tyler B. Smith, Robert S. Hoy, Nikos Ch. Karayiannis. 2014-06-06. Effect of chain stiffness on the competition between crystallization and glass-formation in model colloidal polymers. https://doi.org/10.1063/1.4932193

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