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

    19 Citations (Scopus)


    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
    Issue number13-14
    Publication statusPublished - 2005
    MoE publication typeA1 Journal article-refereed


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


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