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Microstructural and molecular level characterisation of plastic crystal phases of pyrrolidinium trifluoromethanesulfonyl salts

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journal contribution
posted on 02.12.2002, 00:00 authored by A Hill, J Huang, Jim Efthimiadis, P Meakin, Maria ForsythMaria Forsyth, D MacFarlane
Ambient temperature conductive plastic crystal phases of alkylmethylpyrrolidinium trifluoromethanesulfonyl amide (TFSA) salts are studied using positron annihilation lifetime spectroscopy (PALS) to examine the role of vacancy size and concentration in conductivity. The ethyl methylpyrrolidinium TFSA salt (P12 TFSA) has larger vacancies and a greater concentration of vacancies than the dimethylpyrrolidinium TFSA salt (P11 TFSA) over the temperature range investigated. The relative vacancy size and concentration vary with temperature and reflect the solid–solid transitions as measured by differential scanning calorimetry (DSC). P12 TFSA has greater conductivity than P11 TFSA and has furthermore been observed to exhibit slip planes at room temperature. P12 TFSA has greater entropy changes associated with solid–solid phase transitions below the melting point than P11 TFSA possibly indicating greater rotational freedom in P12 TFSA. These results support the notion that the diffusion, conduction, and plastic flow properties of the pyrrolidinium TFSA salts are derived from the lattice vacancies.

History

Journal

Solid state ionics

Volume

154-155

Pagination

119 - 124

Publisher

Elsevier

Location

Amsterdam, The Netherlands

ISSN

0167-2738

eISSN

1872-7689

Language

eng

Publication classification

C1.1 Refereed article in a scholarly journal

Copyright notice

2002, Elsevier Science B.V.