Morphological Control of Helical Structures of an ABC-Type Triblock Terpolymer by Distribution Control of a Blending Homopolymer in a Block Copolymer Microdomain

Higuchi, Takeshi; Sugimori, Hidekazu; Jiang, Xi; Hong, Song; Matsunaga, Kazuyuki; Kaneko, Takeshi; Abetz, Volker; Takahara, Atsushi; Jinnai, Hiroshi

doi:10.1021/ma401193u

Cited by 60 publications

(62 citation statements)

References 37 publications

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“…Relatively recent additions to these categories include the Fddd network [ 5,6 ] and the Frank-Kasper σ phase. [ 7 ] Chemical addition of a third dissimilar block to an AB diblock copolymer yields an ABC copolymer, which, depending on block lengths and incompatibilities, can exhibit significantly enriched phase behavior by microphase-ordering into various combinations of the morphologies listed above, [ 2,[8][9][10] as well as morphologies that are unique to ABC copolymers (e.g., the knitting pattern [ 11 ] and twisted helices [ 12,13 ] ).Recent developments regarding charged multiblock copolymers that can form physical networks and exhibit robust mechanical properties herald new and exciting opportunities for contemporary technologies requiring amphiphilic attributes. Due to the presence of strong interactions, however, control over the phase behavior of such materials remains challenging, especially since their morphologies can be solvent-templated.…”

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confidence: 99%

Morphological Investigation of Midblock‐Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity

Mineart

Jiang

Jinnai

et al. 2014

Macromol. Rapid Commun.

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Recent developments regarding charged multiblock copolymers that can form physical networks and exhibit robust mechanical properties herald new and exciting opportunities for contemporary technologies requiring amphiphilic attributes. Due to the presence of strong interactions, however, control over the phase behavior of such materials remains challenging, especially since their morphologies can be solvent-templated. In this study, transmission electron microscopy and microtomography are employed to examine the morphological characteristics of midblock-sulfonated pentablock ionomers prepared from solvents differing in polarity. Resultant images confirm that discrete, spherical ion-rich microdomains form in films cast from a relatively nonpolar solvent, whereas an apparently mixed morphology with a continuous ion-rich pathway is generated when the casting solvent is more highly polar. Detailed 3D analysis of the morphological characteristics confirms the coexistence of hexagonally-packed nonpolar cylinders and lamellae, which facilitates the diffusion of ions and/or other polar species through the nanostructured medium.

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confidence: 99%

Morphological Investigation of Midblock‐Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity

Mineart

Jiang

Jinnai

et al. 2014

Macromol. Rapid Commun.

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“…Depending on the copolymer composition, the helical structures can be double-, triple-, and to a lower extent, four-stranded as well as a mixture of them. [44] Although the exact structure cannot be distinguished by TEM, the relatively high volume fraction of PS (Table 1) leads to the assumption that the triple helix predominates. The TEM image of neat ISM (Figure 1a) shows a [63] supporting the Ia3d symmetry of the gyroid morphology.…”

Section: Resultsmentioning

confidence: 99%

“…[42,43] Higuchi et al used blending to observe the passing from a double-to triple-and even to four-stranded helical structure of a SBM triblock terpolymer with a polystyrene core cylinder, by adding continuously small amounts of polystyrene homopolymer. [44] Blending triblock terpolymers with homopolymers was also used to complement phase transition studies. [45] When studying binary blends of AB diblock copolymers, ordered structures different from the expected for neat AB diblock copolymers can be found.…”

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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“…The crystallization of mixtures combining block copolymer with semi-crystalline homopolymers is more complicated than that of homopolymer/homopolymer blends [17][18][19][20]. It was found that PMMA or P2VP almost had no influence on the spherulite size of PVDF but significantly decreased the degree of crystallinity.…”

Section: Introductionmentioning

confidence: 99%

Crystallization behaviors of poly(vinylidene fluoride) and poly(methyl methacrylate)-block-poly(2-vinyl pyridine) block copolymer blends

Wang

Chen

2016

J Therm Anal Calorim

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In this study, blends of poly(vinylidene fluoride) and different contents of poly(methyl methacrylate)-block-poly(2-vinyl pyridine) block copolymer (BCP) (PMMA-b-P2VP) are prepared by solution mixing. The phase separation and crystallization behaviors of PVDF and PMMA-b-P2VP blends were characterized by X-ray scattering from small angle to wide angle at different annealing temperatures. The non-isothermal crystallization kinetics of the blends is investigated by differential scanning calorimetry (DSC). During the non-isothermal cooling process, PVDF in blends has higher onset crystallization temperature than that of pure PVDF, which may be attributed to a weak phase separation seen from X-ray scattering patterns, in favor of the nucleation of PVDF. A unique crystallization behavior in DSC test is that as the PVDF content in the blends is dispersed as 30 mass%, degree of crystallinity turns out to be the highest among the blends, even higher than PVDF itself, although the crystallization rate is decreasing with the BCP content. By a novel treatment of dividing the X t * t plot to three stages, it can be found that the relative degree of crystallinity at the end of nucleation process can be responsible for the unusual crystallization behavior. Incorporation of BCP definitely increases the hydrophilic property of PVDF materials by water contact angle test. Understanding of PVDF crystallization in the system with BCP guides the further development of high-performance PVDF membrane materials.

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Morphological Control of Helical Structures of an ABC-Type Triblock Terpolymer by Distribution Control of a Blending Homopolymer in a Block Copolymer Microdomain

Cited by 60 publications

References 37 publications

Morphological Investigation of Midblock‐Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity

Morphological Investigation of Midblock‐Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity

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

Crystallization behaviors of poly(vinylidene fluoride) and poly(methyl methacrylate)-block-poly(2-vinyl pyridine) block copolymer blends

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