Issue 69, 2020

High-throughput morphology mapping of self-assembling ternary polymer blends


Multicomponent blending is a convenient yet powerful approach to rationally control the material structure, morphology, and functional properties in solution-deposited films of block copolymers and other self-assembling nanomaterials. However, progress in understanding the structural and morphological dependencies on blend composition is hampered by the time and labor required to synthesize and characterize a large number of discrete samples. Here, we report a new method to systematically explore a wide composition space in ternary blends. Specifically, the blend composition space is divided into gradient segments deposited sequentially on a single wafer by a new gradient electrospray deposition tool, and characterized using high-throughput grazing-incidence small-angle X-ray scattering. This method is applied to the creation of a ternary morphology diagram for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymer blended with PS and PMMA homopolymers. Using “wet brush” homopolymers of very low molecular weight (∼1 kg mol−1), we identify well-demarcated composition regions comprising highly ordered cylinder, lamellae, and sphere morphologies, as well as a disordered phase at high homopolymer mass fractions. The exquisite granularity afforded by this approach also helps to uncover systematic dependencies among self-assembled morphology, topological grain size, and domain period as functions of homopolymer mass fraction and PS : PMMA ratio. These results highlight the significant advantages afforded by blending low molecular weight homopolymers for block copolymer self-assembly. Meanwhile, the high-throughput, combinatorial approach to investigating nanomaterial blends introduced here dramatically reduces the time required to explore complex process parameter spaces and is a natural complement to recent advances in autonomous X-ray characterization.

Graphical abstract: High-throughput morphology mapping of self-assembling ternary polymer blends

Supplementary files

Article information

Article type
05 Oct 2020
13 Nov 2020
First published
24 Nov 2020
This article is Open Access
Creative Commons BY license

RSC Adv., 2020,10, 42529-42541

High-throughput morphology mapping of self-assembling ternary polymer blends

K. Toth, C. O. Osuji, K. G. Yager and G. S. Doerk, RSC Adv., 2020, 10, 42529 DOI: 10.1039/D0RA08491C

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