Self-assembly and flow alignment of protonically conducting complexes of polystyrene-block-poly(4-vinylpyridine) diblock copolymer with phosphoric acid

Mari Tiitu, Mika Torkkeli, Ritva Serimaa, Tapio Mäkelä, Olli T. Ikkala (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

18 Citations (Scopus)

Abstract

Phosphoric acid (H3PO4) is selectively swollen in polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer within its P4VP domains to achieve protonically conducting self-assembled acid–base complexes. Shear flow is imposed to macroscopically align the local self-assembled structures. The materials are characterized using Fourier transformation infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), dynamic rheology, and impedance spectroscopy. Homopolymeric P4VP(H3PO4)x (where x denotes the nominal number of H3PO4 molecules vs. repeat units of P4VP) reaches the conductivity value ca. 5 * 10− 3 S/cm at 100 °C when x approaches the values x = 2.0 ⋯ 2.5. By incorporating a P4VP(H3PO4)2.2 block within PS-block-P4VP (with the block lengths 35.5 and 3.6 kD for PS and P4VP, respectively; polydispersity 1.06), lamellar protonically conducting nanochannels are formed with periodicity of ca. 450 Å based on SAXS. Large-amplitude oscillatory shear flow is applied, which leads to macroscopically rather highly aligned lamellar nanochannels based on SAXS. Surprisingly, this leads to only slightly anisotropic conductivities. For example, at 100 °C conductivity of 5 * 10− 6 S/cm along the channels and 7 * 10− 7 S/cm in the perpendicular direction are obtained. The observations indicate that defects, potentially involving “dead-end channels” may control the transport properties in self-assembled and aligned materials across macroscopic dimensions.
Original languageEnglish
Pages (from-to)1291 - 1299
Number of pages9
JournalSolid State Ionics
Volume176
Issue number13-14
DOIs
Publication statusPublished - 2005
MoE publication typeA1 Journal article-refereed

Fingerprint

phosphoric acid
Phosphoric acid
X ray scattering
Self assembly
Block copolymers
self assembly
Polystyrenes
polystyrene
copolymers
alignment
Shear flow
shear flow
conduction
conductivity
scattering
x rays
Fourier transformation
Polydispersity
Rheology
rheology

Keywords

  • self-assembly
  • block copolymers
  • phosphoric acid
  • acid-base salt
  • proton conductivity
  • flow alignment
  • polymers
  • proton conduction

Cite this

@article{c332398eb4b343a1a68f1939f0421bc1,
title = "Self-assembly and flow alignment of protonically conducting complexes of polystyrene-block-poly(4-vinylpyridine) diblock copolymer with phosphoric acid",
abstract = "Phosphoric acid (H3PO4) is selectively swollen in polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer within its P4VP domains to achieve protonically conducting self-assembled acid–base complexes. Shear flow is imposed to macroscopically align the local self-assembled structures. The materials are characterized using Fourier transformation infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), dynamic rheology, and impedance spectroscopy. Homopolymeric P4VP(H3PO4)x (where x denotes the nominal number of H3PO4 molecules vs. repeat units of P4VP) reaches the conductivity value ca. 5 * 10− 3 S/cm at 100 °C when x approaches the values x = 2.0 ⋯ 2.5. By incorporating a P4VP(H3PO4)2.2 block within PS-block-P4VP (with the block lengths 35.5 and 3.6 kD for PS and P4VP, respectively; polydispersity 1.06), lamellar protonically conducting nanochannels are formed with periodicity of ca. 450 {\AA} based on SAXS. Large-amplitude oscillatory shear flow is applied, which leads to macroscopically rather highly aligned lamellar nanochannels based on SAXS. Surprisingly, this leads to only slightly anisotropic conductivities. For example, at 100 °C conductivity of 5 * 10− 6 S/cm along the channels and 7 * 10− 7 S/cm in the perpendicular direction are obtained. The observations indicate that defects, potentially involving “dead-end channels” may control the transport properties in self-assembled and aligned materials across macroscopic dimensions.",
keywords = "self-assembly, block copolymers, phosphoric acid, acid-base salt, proton conductivity, flow alignment, polymers, proton conduction",
author = "Mari Tiitu and Mika Torkkeli and Ritva Serimaa and Tapio M{\"a}kel{\"a} and Ikkala, {Olli T.}",
year = "2005",
doi = "10.1016/j.ssi.2005.02.018",
language = "English",
volume = "176",
pages = "1291 -- 1299",
journal = "Solid State Ionics",
issn = "0167-2738",
publisher = "Elsevier",
number = "13-14",

}

Self-assembly and flow alignment of protonically conducting complexes of polystyrene-block-poly(4-vinylpyridine) diblock copolymer with phosphoric acid. / Tiitu, Mari; Torkkeli, Mika; Serimaa, Ritva; Mäkelä, Tapio; Ikkala, Olli T. (Corresponding Author).

In: Solid State Ionics, Vol. 176, No. 13-14, 2005, p. 1291 - 1299.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Self-assembly and flow alignment of protonically conducting complexes of polystyrene-block-poly(4-vinylpyridine) diblock copolymer with phosphoric acid

AU - Tiitu, Mari

AU - Torkkeli, Mika

AU - Serimaa, Ritva

AU - Mäkelä, Tapio

AU - Ikkala, Olli T.

PY - 2005

Y1 - 2005

N2 - Phosphoric acid (H3PO4) is selectively swollen in polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer within its P4VP domains to achieve protonically conducting self-assembled acid–base complexes. Shear flow is imposed to macroscopically align the local self-assembled structures. The materials are characterized using Fourier transformation infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), dynamic rheology, and impedance spectroscopy. Homopolymeric P4VP(H3PO4)x (where x denotes the nominal number of H3PO4 molecules vs. repeat units of P4VP) reaches the conductivity value ca. 5 * 10− 3 S/cm at 100 °C when x approaches the values x = 2.0 ⋯ 2.5. By incorporating a P4VP(H3PO4)2.2 block within PS-block-P4VP (with the block lengths 35.5 and 3.6 kD for PS and P4VP, respectively; polydispersity 1.06), lamellar protonically conducting nanochannels are formed with periodicity of ca. 450 Å based on SAXS. Large-amplitude oscillatory shear flow is applied, which leads to macroscopically rather highly aligned lamellar nanochannels based on SAXS. Surprisingly, this leads to only slightly anisotropic conductivities. For example, at 100 °C conductivity of 5 * 10− 6 S/cm along the channels and 7 * 10− 7 S/cm in the perpendicular direction are obtained. The observations indicate that defects, potentially involving “dead-end channels” may control the transport properties in self-assembled and aligned materials across macroscopic dimensions.

AB - Phosphoric acid (H3PO4) is selectively swollen in polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer within its P4VP domains to achieve protonically conducting self-assembled acid–base complexes. Shear flow is imposed to macroscopically align the local self-assembled structures. The materials are characterized using Fourier transformation infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), dynamic rheology, and impedance spectroscopy. Homopolymeric P4VP(H3PO4)x (where x denotes the nominal number of H3PO4 molecules vs. repeat units of P4VP) reaches the conductivity value ca. 5 * 10− 3 S/cm at 100 °C when x approaches the values x = 2.0 ⋯ 2.5. By incorporating a P4VP(H3PO4)2.2 block within PS-block-P4VP (with the block lengths 35.5 and 3.6 kD for PS and P4VP, respectively; polydispersity 1.06), lamellar protonically conducting nanochannels are formed with periodicity of ca. 450 Å based on SAXS. Large-amplitude oscillatory shear flow is applied, which leads to macroscopically rather highly aligned lamellar nanochannels based on SAXS. Surprisingly, this leads to only slightly anisotropic conductivities. For example, at 100 °C conductivity of 5 * 10− 6 S/cm along the channels and 7 * 10− 7 S/cm in the perpendicular direction are obtained. The observations indicate that defects, potentially involving “dead-end channels” may control the transport properties in self-assembled and aligned materials across macroscopic dimensions.

KW - self-assembly

KW - block copolymers

KW - phosphoric acid

KW - acid-base salt

KW - proton conductivity

KW - flow alignment

KW - polymers

KW - proton conduction

U2 - 10.1016/j.ssi.2005.02.018

DO - 10.1016/j.ssi.2005.02.018

M3 - Article

VL - 176

SP - 1291

EP - 1299

JO - Solid State Ionics

JF - Solid State Ionics

SN - 0167-2738

IS - 13-14

ER -