Favorable polymer-substrate interactions induce surface orientation fields in block copolymer (BCP) melts. In linear BCP processed near equilibrium, alignment of domains generally persists for a small number of periods (∼4–6 D 0 ) before randomization of domain orientation. Bottlebrush BCP are an emerging class of materials with distinct chain dynamics stemming from substantial molecular rigidity, enabling rapid assembly at ultrahigh (>100 nm) domain periodicities with strong photonic properties (structural color). This work assesses interface-induced ordering in PS- b -PLA bottle b rush diblock copolymer films during thermal annealing between planar surfaces. To clearly observe the decay in orientational order from surface to bulk, we choose to study micron-scale films spanning greater than 200 lamellar periods. In situ optical microscopy and transmission UV-Vis spectroscopy are used to monitor photonic properties during annealing and paired with ex situ UV-Vis reflection measurement, cross-sectional scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS) to probe the evolution of domain microstructure. Photonic properties were observed to saturate within minutes of annealing at 150 °C, with distinct variation in transmission response as a function of film thickness. The depth of the highly aligned surface region was found to vary stochastically in the range of 30–100 lamellar periods, with the sharpness of the orientation gradient decreasing substantially with increasing film thickness. This observation suggests a competition between growth of aligned, heterogeneously nucleated, grains at the surface and orientationally isotropic, homogeneously nucleated, grains throughout the bulk. This work demonstrates the high potential of bottlebrush block copolymers in rapid fabrication workflows and provides a point of comparison for future application of directed self-assembly to BBCP ordering.
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Evolution of elliptical SAXS patterns in aligned systems
Small-angle X-ray and neutron scattering (SAXS and SANS) patterns from certain semicrystalline polymers and liquid crystals contain discrete reflections from ordered assemblies and central diffuse scattering (CDS) from uncorrelated structures. Systems with imperfectly ordered lamellar structures aligned by stretching or by a magnetic field produce four distinct SAXS patterns: two-point `banana', four-point pattern, four-point `eyebrow' and four-point `butterfly'. The peak intensities of the reflections lie not on a layer line, or the arc of a circle, but on an elliptical trajectory. Modeling shows that randomly placed lamellar stacks modified by chain slip and stack rotation or interlamellar shear can create these forms. On deformation, the isotropic CDS becomes an equatorial streak with an oval, diamond or two-bladed propeller shape, which can be analyzed by separation into isotropic and oriented components. The streak has elliptical intensity contours, a natural consequence of the imperfect alignment of the elongated scattering objects. Both equatorial streaks and two- and four-point reflections can be fitted in elliptical coordinates with relatively few parameters. Equatorial streaks can be analyzed to obtain the size and orientation of voids, fibrils or surfaces. Analyses of the lamellar reflection yield lamellar spacing, stack orientation (interlamellar shear) angle α and chain slip angle ϕ, as well as the size distribution of the lamellar stacks. Currently available computational tools allow these microstructural parameters to be rapidly refined.
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- Award ID(s):
- 2118860
- PAR ID:
- 10542077
- Editor(s):
- Sato, TJ
- Publisher / Repository:
- International Union of Crystallography
- Date Published:
- Journal Name:
- Journal of Applied Crystallography
- Volume:
- 57
- Issue:
- 4
- ISSN:
- 1600-5767
- Page Range / eLocation ID:
- 1127 to 1136
- Subject(s) / Keyword(s):
- aligned objects lamellar arrays semicrystalline polymers small-angle X-ray scattering elliptical traces.
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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