The Formation of OTDD Network Structure in PS‐<i>b</i>‐PI‐<i>b</i>‐PDMS Triblock Terpolymer

Wang, Yi-Chin; Inoue, Ayano; Hasegawa, Hirokazu; Takenaka, Mikihito

doi:10.1002/macp.201700008

Cited by 6 publications

(8 citation statements)

References 29 publications

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“…Since this pioneering work, many other BCP structures have been investigated by TEMT, including the rediscovery and validation of the OBDD (see Figure 18) in a number of BCP systems including BCP blends 127 as well as fascinating order−order thermotropic transformations between the DD and DG in diblocks of polystyrene and syndiotactic polypropylene. 128,129 While current TEMT methodology can ascertain the 3D connectivity of complex structures, there are limitations on the fidelity of the reconstructed structure, particularly the detailed shape of the IMDS and the associated subdomain thicknesses. These limitations include the detrimental influence of the "missing wedge" of information in the reconstruction due to the inability to acquire 2D projections of the thin sample over the full tilt angle due to the geometric limitations of the microscope goniometer stage and multiple scattering at high tilt angles since the beam path along the projection direction grows with tilt (i.e., as secant of angle).…”

Section: Measurements Of Bcp Morphology: Frommentioning

confidence: 99%

“…This 3D reconstruction permitted, for the first time, measurement of the IMDS curvature, node functionality, Euler characteristic, and associated topological genus value. Since this pioneering work, many other BCP structures have been investigated by TEMT, including the rediscovery and validation of the OBDD (see Figure ) in a number of BCP systems including BCP blends as well as fascinating order–order thermotropic transformations between the DD and DG in diblocks of polystyrene and syndiotactic polypropylene. , …”

Section: Measurements Of Bcp Morphology: From Supradomain Periodicity...mentioning

confidence: 99%

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Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

et al. 2021

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Block copolymer (BCP) melts are a paradigm for pluripotent molecular assembly, yielding a complex and expanding array of variable domain shapes and symmetries from a fairly simple and highly expandable class of molecular designs. This Perspective addresses recent advances in the ability to model and measure features of domain morphology that go beyond the now canonical metrics of D spacing, space group, and domain topology. Such subdomain features have long been the focus of theories seeking to explain and understand mechanisms of equilibrium structure formation in block copolymer melts, from inhomogeneous curvatures of an intermaterial dividing surface to variable domain thickness. Quantitative metrics of variable subdomain geometry, or packing frustration, are central to theoretical models of complex BCP phase formation, from bicontinuous networks to complex (e.g., Frank–Kasper) crystals, and new experimental methods bring the possibility of their quantitative tests into reach. Here we not only review generic approaches to quantify local domain morphologies that both connect directly to thermodynamic models of BCP assembly but also generalize to domains of arbitrary shape and topology. We then overview experimental methods for characterizing BCP morphology, focusing on recent advances that make accessible detailed and quantitative metrics of fine features of subdomain geometry. Beyond even the critical comparison between detailed predictive models and experimental measurements of complex BCP assembly, validation of these advances lays the foundation to “mold” morphology in BCP assemblies at ever finer subdomain scale, through controlled architectures and processing pathways.

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Section: Measurements Of Bcp Morphology: Frommentioning

confidence: 99%

Section: Measurements Of Bcp Morphology: From Supradomain Periodicity...mentioning

confidence: 99%

Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

et al. 2021

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“… 5 Examples include helical structures, 6 core–shell gyroid morphologies, 7 and tricontinuous double-diamond structures. 8 For obtaining three-phase morphologies, but avoiding the challenging synthesis that is accompanied by the preparation of terpolymers, several research groups have investigated the phase behavior of copolymer blends, either with interacting 9 − 11 or noninteracting polymer pairs. 12 − 15 …”

mentioning

confidence: 99%

“…Copolymers with a more complex macromolecular architecture often give rise to more complex self-assembly. , While microphase separation of diblock copolymers is limited to spherical, cylindrical, lamellar and gyroid structures, over 30 different phases have been identified for linear triblock terpolymers . Examples include helical structures, core–shell gyroid morphologies, and tricontinuous double-diamond structures . For obtaining three-phase morphologies, but avoiding the challenging synthesis that is accompanied by the preparation of terpolymers, several research groups have investigated the phase behavior of copolymer blends, either with interacting − or noninteracting polymer pairs. − …”

mentioning

confidence: 99%

“…5 Examples include helical structures, 6 core−shell gyroid morphologies, 7 and tricontinuous double-diamond structures. 8 For obtaining three-phase morphologies, but avoiding the challenging synthesis that is accompanied by the preparation of terpolymers, several research groups have investigated the phase behavior of copolymer blends, either with interacting 9−11 or noninteracting polymer pairs. 12−15 An alternative approach is the use of surfactants that associate with a certain polymer through hydrogen bonding or electrostatic interactions, thereby resulting in a supramolecular comb-shaped copolymer.…”

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confidence: 99%

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Hierarchical Self-Assembly of Supramolecular Double-Comb Triblock Terpolymers

et al. 2018

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Involving supramolecular chemistry in self-assembling block copolymer systems enables design of macromolecular architectures that are challenging to obtain through conventional all-covalent routes. In this work we present supramolecular double-comb triblock terpolymers in which both outer blocks are able to interact with a surfactant via hydrogen bonding and thereby form a comb-shaped architecture upon complexation. While the neat triblock terpolymer only formed a triple lamellar morphology, multiple hierarchical structures were observed in these supramolecular comb–coil–comb triblock terpolymers by simply adjusting the surfactant concentration. Structures included spheres on tetragonally packed cylinders-in-lamellae and spheres on double parallel lamellae-in-lamellae, as evidenced by electron microscopy and X-ray scattering. Incorporation of a middle coil block thus allowed an even higher macromolecular complexity than the previously reported double-comb diblock copolymers.

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Core–Shell Double Gyroids Directed by Selective Solvation for ABC Triblock Terpolymers

Miyamori,

Tong,

Nabae

et al. 2024

Macromol. Rapid Commun.

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The formation of ABC triblock terpolymers through solution casting is still challenging. In this study, we fabricated core‐shell double gyroid network structures via solution casting using poly(2,2,2‐trifluoroethyl methacrylate)‐b‐poly(4‐vinylpyridine)‐b‐polystyrene (FPS) triblock terpolymers in N,N‐dimethylformamide (DMF). Upon heat treatment, the polymer tended to form a sphere‐in‐lamellar structure at the F/S interface. Given the solubility properties of each component in DMF, it was anticipated that the effective volume fraction of F relative to P would increase in concentrated solutions and the effective volume fraction of S would decrease. The microphase‐separated structure derived from the DMF solution consistently resulted in the formation of a network structure composed of a core‐shell double gyroid, with F as the matrix, P as the shell, and S as the core, and their periodic lengths gradually increased to 110.8, 131.8, and 162.7 nm as increase molecular weight of PS blocks to 13.8, 20.7, and 28.8 kg mol−1. Based on the solubility properties of the polymer components highlighted in this study, the solvent selection strategy is broadly applicable to ABC triblock terpolymers featuring various polymer components, offering a more efficient avenue for fabricating core‐shell double gyroid structures.This article is protected by copyright. All rights reserved

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The Formation of OTDD Network Structure in PS‐b‐PI‐b‐PDMS Triblock Terpolymer

Cited by 6 publications

References 29 publications

Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale

Hierarchical Self-Assembly of Supramolecular Double-Comb Triblock Terpolymers

Core–Shell Double Gyroids Directed by Selective Solvation for ABC Triblock Terpolymers

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