Morphology of ABC Triblock Copolymers

Zheng, Wei; Wang, Zhen‐Gang

doi:10.1021/ma00125a026

Cited by 294 publications

(286 citation statements)

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“…2B) and the ABCB connectivity required by the expected three-domain microstructure, LAM 3 ( Fig. 2C) (8,9). The conflict between LAM 3 and the pattern observed by TEM can only be resolved by invoking partial mixing between the A and C end blocks, apparently driven by low-χ interactions (χ AC K 0).…”

Section: Resultsmentioning

confidence: 93%

“…Extension to higher-order multiblock polymers introduces additional interaction parameters (χ ij ) that impact self-assembly and properties (7). For example, introducing a mutually incompatible C block (χ AC > 0, χ BC > 0) generates a host of new morphologies dictated by the chain connectivity (ABC, ACB, or BAC) and intrinsic χ ij -values (8,9). In this rich phase space, designing multiblock polymers with a combination of miscible and immiscible blocks can also access new structures and impart useful functions (10,11).…”

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confidence: 99%

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Manipulating the ABCs of self-assembly via low-χ block polymer design

Chang

Bates

Lee

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ ij ). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ AC ≲ 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAM P . Transmission electron microscopy indicates that LAM P exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM 3 ) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAM P is thermodynamically stable below a critical χ AC , above which LAM 3 emerges. Both experiments and theory expose close analogies to ABA′ triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.block polymer | self-assembly | polymer nanostructure | domain spacing | LAM P B lock polymers are a diverse class of soft materials capable of self-assembling into complex periodic nanostructures. Synthetic command over composition, dispersity, sequence, and molecular architecture enables control over the mesoscopic order and macroscopic thermal, mechanical, rheological, and transport properties (1-4). The phase behavior of "simple" linear AB diblock copolymers is universally parameterized by the segregation strength χ AB N and relative volume fraction f, where χ AB represents the effective Flory-Huggins binary interaction parameter and N is the total volume-averaged degree of polymerization. Mixing behavior, captured through the mean-field concept of χ AB , is central to block polymer self-assembly: the competing demands of minimizing interfacial energy and maximizing configurational entropy only favor microphase separation when A-B interactions are repulsive (χ AB > 0) (5, 6). Extension to higher-order multiblock polymers introduces additional interaction parameters (χ ij ) that impact self-assembly and properties (7). For example, introducing a mutually incompatible C block (χ AC > 0, χ BC > 0) generates a host of new morphologies dictated by the chain connectivity (ABC, ACB, or BAC) and intrinsic χ ij -values (8, 9). In this rich phase space, designing multiblock polymers with a combination of miscible and immiscible blocks can also access new structures and impart useful functions (10, 11). Perhaps the best-known examples of such systems are linear ABA′ triblock copolymers (χ AB > 0, χ AA′ ≈ 0): their high-value industrial applications as thermoplastic elastomers are entirely enabled by A/A′ mixing and chain connectivity, which together create physically cross-linked materials with ex...

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Section: Resultsmentioning

confidence: 93%

mentioning

confidence: 99%

Manipulating the ABCs of self-assembly via low-χ block polymer design

Chang

Bates

Lee

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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“…19 A comprehensive theoretical use. The polymerizations were carried out in 250 study on ABC triblock copolymers 20 predicted mL round-bottom flasks bearing three groundthat the block sequence should have a dramatic glass joints each fitted with a rubber septum. Cateffect altering the solid-state morphology of an alytic amounts (Ç 20 mg) of TBABB catalyst were equimolar triblock from lamellar, to cylinders in transferred to the polymerization flask, which lamellae, and to cylinders surrounded by rings.…”

Section: Introductionmentioning

confidence: 99%

ABC triblock polymethacrylates: Group transfer polymerization synthesis of the ABC, ACB, and BAC topological isomers and solution characterization

Patrickios

Lowe

Armes

et al. 1998

J. Polym. Sci. A Polym. Chem.

102

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“…200,203,278,279 By increasing the complexity of the system to the trench edge. In addition, the grain size of the square pattern could be greatly increased to several microns.…”

Section: Self-assembly Of Linear Pfs Triblock Terpolymers To Form Phamentioning

confidence: 99%