Formation of Tetragonally-Packed Rectangular Cylinders from ABC Block Terpolymer Blends

Asai, Yusuke; Yamada, Kotaro; Yamada, Mutsuhiko; Takano, Atsushi; Matsushita, Yushu

doi:10.1021/mz400647v

Cited by 38 publications

(73 citation statements)

References 28 publications

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“…Another striking example where marked multimodal dispersity was able to produce a very specific morphology by selected chain location was reported by Asai et al [ 15 ] in a 2014 paper. In this work, ISP polymers having the same molar mass (≈120 kg mol −1 ), the same middle‐block volume fraction, but a marked difference in end‐block volume fraction (volume fractions of PI:PS:P2VP equal to 0.39:0.56:0.05, and 0.06:0.62:0.32) were mixed.…”

Section: From Monomodal To Multimodal Dispersity Using Blends Of Blocmentioning

confidence: 99%

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Nonclassical Block Copolymer Self‐Assembly Resulting from a Constrained Location of Chains and Junctions

Matsushita

Takano

Vayer

et al. 2020

Adv Materials Inter

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During the self‐assembly process of block copolymers, interfaces are formed as a result of the microphase separation between the blocks. The location of the polymer chains and block junctions with respect to these interfaces is crucial and drives the morphology. It depends on the dispersities (e.g., molecular mass and composition) of the blocks, their architectures (e.g., linear vs star), and the type of interaction (e.g., repulsion vs attraction). In this review, the authors focus on the formation of unusual morphologies that are obtained in the following three categories: i) multimodal blends of block polymers, ii) star block polymers, and iii) supramolecular assemblies composed of block copolymers. Although these three examples seem to be very different from one another, the authors demonstrate in this review that they all share a constrained location of their chains and/or junctions with respect to the interfaces. In this sense, they deviate from the common behavior of simple linear block copolymers, in which the junctions are located on the interface and homogeneously distributed onto it.

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Section: From Monomodal To Multimodal Dispersity Using Blends Of Blocmentioning

confidence: 99%

“…TEM image, 3D TEM tomography reconstructed image and the schematic illustration of the morphology observed by Asai et al [ 15 ] for a blend of three symmetric PI‐ b ‐PS‐ b ‐P2VP. Reproduced with permission.…”

Section: From Monomodal To Multimodal Dispersity Using Blends Of Blocmentioning

confidence: 99%

Nonclassical Block Copolymer Self‐Assembly Resulting from a Constrained Location of Chains and Junctions

Matsushita

Takano

Vayer

et al. 2020

Adv Materials Inter

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“…With increasing 3-NDP content, spheres on tetragonally packed diamondshaped cylinders-in-lamellae were observed, spheres on double parallel lamellae-in-lamellae, and spheres on double perpendicular lamellae-in-lamellae. Blending of triblock terpolymer morphologies with homopolymers or hydrogen bonded triblock terpolymers of different composition generated unprecedented rectangular cylinders in a tetragonal unit lattice, [58] tetragonally-packed spheres, core/shell double gyroids [59] or rectangular-shaped rods. [60] These blending examples teach that there are likely to be more BCP morphologies hidden in unexplored areas of the ternary microphase diagram as well as hierarchical structures by loading of individual microdomains with small molecular weight additives.…”

Section: Microphase Separation In Bulkmentioning

confidence: 99%

Self‐Assembly of Multiblock Copolymers

Qiang

Chakroun

Janoszka

et al. 2019

Israel Journal of Chemistry

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Block copolymers (BCPs) are a subclass of soft matter extensively used in materials science and nanomedicine. They consist of two or more incompatible segments and are prone to self‐assemble into nanostructures with a characteristic size of 10–100 nm. BCPs thus naturally address the structural dimension between molecular and colloidal scales. This review gives a brief overview of recent developments in BCP self‐assembly under various conditions. Special emphasis is put on linear BCPs with three or more sequentially linked blocks, i. e. ABC triblock terpolymers, ABAC tetrablock terpolymers, and so on. We discuss their microphase separation in bulk, in the confinement of nanoemulsion droplets, and their hierarchical self‐assembly to multicompartment nanostructures in selective solvents. Regarding applications, block copolymers are widely used in templating and drug delivery, but their inherent asymmetry is also particularly useful for the synthesis of Janus nanoparticles.

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“…[40] But blending can also be used to obtain different morphologies starting from neat block copolymers. [41] This is of especial interest if a certain desired morphology is difficult to achieve because of its appearance in a narrow composition range. For example, the gyroid morphology has been able to be studied more precisely via blending experiments.…”

Section: Introductionmentioning

confidence: 99%

Four‐Phase Morphologies in Blends of ABC and BAC Triblock Terpolymers

Haenelt

Abetz

2017

Macro Chemistry & Physics

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considerably more complex compared to diblock copolymers due to an increased number of variables. Thus, the morphology of linear ABC triblock terpolymers is controlled mainly by three interaction parameters (χ AB , χ AC , χ BC ,) and two independent volume fractions (f A , f B , f C = 1 -f A -f B ), as well as the block sequence. Among the morphologies are lamellae, lamellae with spheres or cylinders, knitting pattern, spheres on sphere, alternating and core-shell double gyroids, cylinder in cylinder, undulated/perforated cylinder in cylinder, cylinder at cylinder, spheres on cylinder, helices on cylinder. [12][13][14][15][16][17][18] The helices on cylinder represents a special case in between these morphologies. On the one hand, it is rare because it can be achieved only in a rather narrow composition window, but what is even more peculiar, it is the self-assembly of a nonchiral block copolymer into a chiral structure. [19] In order to develop functional materials with special electrical, optical, or magnetic properties, multiblock copolymers are promising, because of their capability to self-assemble into complex ordered morphologies, with symmetries like crystalline structures known from low molecular weight inorganic salts. [20] Lee et al. [21,22] were the first to identify a Frank-Kasper σ phase, which is a large tetragonal unit cell with P4 2 /mnm symmetry and 30 spheres, [23,24] in linear block copolymers. From then on numerous studies about novel sphere-forming morphologies in AB diblock [25][26][27] copolymers and ABAC tetrablock terpolymers [28] have been published. Especially linear ABAC tetrablock terpolymers are promising for the investigation of new structures. [29] Chanpuriya et al. [30] have presented nine different spherical phases for tetrablock terpolymers.Controlling the morphology for a given block copolymer by changing the volume fractions of the corresponding blocks implies the synthesis of one block copolymer for each morphology. There are other, more readily available methods to achieve different morphologies starting from one block copolymer. One method implicates chemical postmodification, like complexation or hydrogenation. Bronstein et al. [31] have modified the polybutadiene block (PB) of a polystyreneblock-polybutadiene-block-poly(methyl methacrylate) (SBM) triblock terpolymer by complexation with transition metal complexes, like Fe-complex and Pd-complex. They were able to observe a change from a lamellar morphology before modification to a cylindrical or gyroid morphology after the Blends It is investigated how binary blends of two asymmetric triblock terpolymers with the same type of monomers but different block sequences (ABC, BAC) and different block lengths lead to three new ABAC tetrablock terpolymer like morphologies. This study ascribes the formation of four microphases to a parallel chain orientation during the blend process. Because of the resultant spatial superposition, the B-blocks of both block copolymers can mix into each other as well as both C-blocks, whereas bot...

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Formation of Tetragonally-Packed Rectangular Cylinders from ABC Block Terpolymer Blends

Cited by 38 publications

References 28 publications

Nonclassical Block Copolymer Self‐Assembly Resulting from a Constrained Location of Chains and Junctions

Nonclassical Block Copolymer Self‐Assembly Resulting from a Constrained Location of Chains and Junctions

Self‐Assembly of Multiblock Copolymers

Four‐Phase Morphologies in Blends of ABC and BAC Triblock Terpolymers

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