Formation of tiling patterns in hierarchical structures through self-assembly of ABCD miktoarm star quaterpolymers.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41082255.
- Also identified by DOI 10.1039/d5sm00880h.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
Block copolymers are a key class of soft matter, and their ability to form complex nanostructures is dictated by molecular architecture and block composition. In this study, we investigate the self-assembled structures of ABCD miktoarm star quaterpolymers using simulated annealing. By systematically tuning the volume fraction of the longest arm (D-arm), <i>f</i><sub>D</sub>, while keeping the ratio <i>f</i><sub>A</sub> : <i>f</i><sub>B</sub> : <i>f</i><sub>C</sub> fixed at six representative values, we construct phase diagrams revealing 15 distinct three-dimensional hierarchical ordered microstructures, 14 of which are reported for the first time. At high <i>f</i><sub>D</sub> (∼0.6), we identify six LS<sub>3</sub> structures (an alternating packing of monolayers of "three-color" spheres arranged in tiling patterns and D-lamellae). As <i>f</i><sub>C</sub>/(<i>f</i><sub>A</sub> + <i>f</i><sub>B</sub>) increases, the coordination number of each C-domain increases from 4 to 6 to 8 to 10 and further to 12 in the monolayer. At lower <i>f</i><sub>D</sub>, six CS<sub>3</sub> and three C<sub>2</sub>S<sub>2</sub> structures (composed of "three-color" or "two-color" spherical and "one-color" or "two-color" cylindrical domains) form, exhibiting intricate tiling patterns in the cross-sections of the cylinders and on the curved surfaces of each cylinder in the CS<sub>3</sub> structure. At <i>f</i><sub>A</sub> : <i>f</i><sub>B</sub> : <i>f</i><sub>C</sub> = 1 : 1 : 1, 1 : 1 : 0.5 and 1 : 1 : 2, the patterns undergo sequential transitions of [10.6.4; 10.6.4; 10.6.6] → [8.6.4; 8.6.6] → [6.6.6], [10.6.4; 10.6.4; 10.6.6] → [6.6.6] + [12.6.4] → [8.8.4] and [12.6.4]→ [3.3.4.3.4] → [8.8.4], respectively, with decreasing <i>f</i><sub>D</sub>, where the notation [<i>k</i>.<i>l</i>.<i>m</i>] has the same meaning as that used in the miktoarm star terpolymer systems, except that some cylinders are composed of an alternating arrangement of A-, B- and C-spheres or A- and B-spheres. We elucidate the formation mechanisms of the observed structures based on composition-geometry relationships. This work advances the understanding of self-assembly in multi-arm star copolymers and provides foundational design principles for engineering hierarchical nanomaterials with programmable tiling geometries.