Structural Hierarchy in Flow-Aligned Hexagonally Self-Organized Microphases with Parallel Polyelectrolytic Structures

T. Ruotsalainen, M. Torkkeli, R. . Serimaa, Tapio Mäkelä, R. Mäki-Ontto, J. Ruokolainen, G.ten Brinke (Corresponding Author), O Ikkala (Corresponding Author)

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30 Citations (Scopus)

Abstract

We report a novel structural hierarchy where a flow-aligned hexagonal self-organized structure is combined with a polyelectrolytic self-organization on a smaller length scale and where the two structures are mutually parallel. Polystyrene-block-poly(4-vinylpyridine) (PS-block-P4VP) is selected with a short P4VP block, which is protonated with p-toluenesulfonic acid (TSA) and further hydrogen bonded with 3-n-pentadecylphenol (PDP). To suppress the amount of free (uncomplexed) acid which we expected to have adverse effects during the extended shearing at the elevated temperatures, a safely less than stoichiometric amount of TSA was used, i.e., PS-block-P4VP(TSA)0.9(PDP)1.0. The formation of the supramolecules and the resulting structures were investigated using infrared spectroscopy (FTIR), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). As the weight fraction of P4VP(TSA)0.9(PDP)1.0 is ca. 20%, hexagonal self-organization occurs, as shown by SAXS. Shear flow leads to remarkably well-aligned structures. SAXS also indicates an internal structure within the P4VP(TSA)0.9(PDP)1.0 blocks with a long period of 41 Å. In contrast to the previously observed structural hierarchies in diblock copolymer/amphiphile supramolecules, which contained mutually perpendicular structures, e.g., lamellae within cylinders, in the present case SAXS in combination with models suggests internal polyelectrolytic layers parallel to the hexagonally ordered microphases. These aligned conducting nanochannels also manifest as a slight overall conductivity anisotropy.
Original languageEnglish
Pages (from-to)9437-9442
Number of pages6
JournalMacromolecules
Volume36
Issue number25
DOIs
Publication statusPublished - 2003
MoE publication typeA1 Journal article-refereed

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X ray scattering
Acids
Polystyrenes
Amphiphiles
Shear flow
Shearing
Block copolymers
Hydrogen
Infrared spectroscopy
Anisotropy
Transmission electron microscopy
Temperature
polystyrene-block-poly(4-vinylpyridine)

Cite this

Ruotsalainen, T., Torkkeli, M., . Serimaa, R., Mäkelä, T., Mäki-Ontto, R., Ruokolainen, J., ... Ikkala, O. (2003). Structural Hierarchy in Flow-Aligned Hexagonally Self-Organized Microphases with Parallel Polyelectrolytic Structures. Macromolecules, 36(25), 9437-9442. https://doi.org/10.1021/ma0345955
Ruotsalainen, T. ; Torkkeli, M. ; . Serimaa, R. ; Mäkelä, Tapio ; Mäki-Ontto, R. ; Ruokolainen, J. ; Brinke, G.ten ; Ikkala, O. / Structural Hierarchy in Flow-Aligned Hexagonally Self-Organized Microphases with Parallel Polyelectrolytic Structures. In: Macromolecules. 2003 ; Vol. 36, No. 25. pp. 9437-9442.
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abstract = "We report a novel structural hierarchy where a flow-aligned hexagonal self-organized structure is combined with a polyelectrolytic self-organization on a smaller length scale and where the two structures are mutually parallel. Polystyrene-block-poly(4-vinylpyridine) (PS-block-P4VP) is selected with a short P4VP block, which is protonated with p-toluenesulfonic acid (TSA) and further hydrogen bonded with 3-n-pentadecylphenol (PDP). To suppress the amount of free (uncomplexed) acid which we expected to have adverse effects during the extended shearing at the elevated temperatures, a safely less than stoichiometric amount of TSA was used, i.e., PS-block-P4VP(TSA)0.9(PDP)1.0. The formation of the supramolecules and the resulting structures were investigated using infrared spectroscopy (FTIR), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). As the weight fraction of P4VP(TSA)0.9(PDP)1.0 is ca. 20{\%}, hexagonal self-organization occurs, as shown by SAXS. Shear flow leads to remarkably well-aligned structures. SAXS also indicates an internal structure within the P4VP(TSA)0.9(PDP)1.0 blocks with a long period of 41 {\AA}. In contrast to the previously observed structural hierarchies in diblock copolymer/amphiphile supramolecules, which contained mutually perpendicular structures, e.g., lamellae within cylinders, in the present case SAXS in combination with models suggests internal polyelectrolytic layers parallel to the hexagonally ordered microphases. These aligned conducting nanochannels also manifest as a slight overall conductivity anisotropy.",
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Ruotsalainen, T, Torkkeli, M, . Serimaa, R, Mäkelä, T, Mäki-Ontto, R, Ruokolainen, J, Brinke, GT & Ikkala, O 2003, 'Structural Hierarchy in Flow-Aligned Hexagonally Self-Organized Microphases with Parallel Polyelectrolytic Structures', Macromolecules, vol. 36, no. 25, pp. 9437-9442. https://doi.org/10.1021/ma0345955

Structural Hierarchy in Flow-Aligned Hexagonally Self-Organized Microphases with Parallel Polyelectrolytic Structures. / Ruotsalainen, T.; Torkkeli, M.; . Serimaa, R.; Mäkelä, Tapio; Mäki-Ontto, R.; Ruokolainen, J.; Brinke, G.ten (Corresponding Author); Ikkala, O (Corresponding Author).

In: Macromolecules, Vol. 36, No. 25, 2003, p. 9437-9442.

Research output: Contribution to journalArticleScientificpeer-review

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T1 - Structural Hierarchy in Flow-Aligned Hexagonally Self-Organized Microphases with Parallel Polyelectrolytic Structures

AU - Ruotsalainen, T.

AU - Torkkeli, M.

AU - . Serimaa, R.

AU - Mäkelä, Tapio

AU - Mäki-Ontto, R.

AU - Ruokolainen, J.

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AU - Ikkala, O

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N2 - We report a novel structural hierarchy where a flow-aligned hexagonal self-organized structure is combined with a polyelectrolytic self-organization on a smaller length scale and where the two structures are mutually parallel. Polystyrene-block-poly(4-vinylpyridine) (PS-block-P4VP) is selected with a short P4VP block, which is protonated with p-toluenesulfonic acid (TSA) and further hydrogen bonded with 3-n-pentadecylphenol (PDP). To suppress the amount of free (uncomplexed) acid which we expected to have adverse effects during the extended shearing at the elevated temperatures, a safely less than stoichiometric amount of TSA was used, i.e., PS-block-P4VP(TSA)0.9(PDP)1.0. The formation of the supramolecules and the resulting structures were investigated using infrared spectroscopy (FTIR), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). As the weight fraction of P4VP(TSA)0.9(PDP)1.0 is ca. 20%, hexagonal self-organization occurs, as shown by SAXS. Shear flow leads to remarkably well-aligned structures. SAXS also indicates an internal structure within the P4VP(TSA)0.9(PDP)1.0 blocks with a long period of 41 Å. In contrast to the previously observed structural hierarchies in diblock copolymer/amphiphile supramolecules, which contained mutually perpendicular structures, e.g., lamellae within cylinders, in the present case SAXS in combination with models suggests internal polyelectrolytic layers parallel to the hexagonally ordered microphases. These aligned conducting nanochannels also manifest as a slight overall conductivity anisotropy.

AB - We report a novel structural hierarchy where a flow-aligned hexagonal self-organized structure is combined with a polyelectrolytic self-organization on a smaller length scale and where the two structures are mutually parallel. Polystyrene-block-poly(4-vinylpyridine) (PS-block-P4VP) is selected with a short P4VP block, which is protonated with p-toluenesulfonic acid (TSA) and further hydrogen bonded with 3-n-pentadecylphenol (PDP). To suppress the amount of free (uncomplexed) acid which we expected to have adverse effects during the extended shearing at the elevated temperatures, a safely less than stoichiometric amount of TSA was used, i.e., PS-block-P4VP(TSA)0.9(PDP)1.0. The formation of the supramolecules and the resulting structures were investigated using infrared spectroscopy (FTIR), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). As the weight fraction of P4VP(TSA)0.9(PDP)1.0 is ca. 20%, hexagonal self-organization occurs, as shown by SAXS. Shear flow leads to remarkably well-aligned structures. SAXS also indicates an internal structure within the P4VP(TSA)0.9(PDP)1.0 blocks with a long period of 41 Å. In contrast to the previously observed structural hierarchies in diblock copolymer/amphiphile supramolecules, which contained mutually perpendicular structures, e.g., lamellae within cylinders, in the present case SAXS in combination with models suggests internal polyelectrolytic layers parallel to the hexagonally ordered microphases. These aligned conducting nanochannels also manifest as a slight overall conductivity anisotropy.

U2 - 10.1021/ma0345955

DO - 10.1021/ma0345955

M3 - Article

VL - 36

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JO - Macromolecules

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