Glass transition behaviour of ionic liquid, 1-butyl-3-methylimidazolium
tetrafluoroborate-H2O mixed solutions

Yukihiro Yoshimuraa, Hyosun Kimuraa, Chikara Okamotoa, Tomoki Miyashitaa,Yusuke Imaib, Hiroshi Abeb

aDepartment of Applied Chemistry, National Defense Academy, Yokosuka, Kanagawa 239-8686, Japan
bDepartment of Materials Science and Engineering, National Defense Academy, Yokosuka, Kanagawa 239-8686, Japan

J. Chem. Thermodynamics 43 (2011) 410-412.

Abstract
Here, we have measured the glass transition temperature (Tg) of the ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate-H2O mixed solutions as a function of H2O concentration (x mol% H2O). The glass-forming composition region was also determined. Contrary to the results of the quaternary ammonium type of ionic liquid, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate-H2O mixed solutions, we did not observed the multiple glass transition behaviour. We also measured the glassy Raman spectra of the solutions at T = 77 K.We find that the eenearly freeff hydrogen bonded Raman band of water molecules in the aqueous [bmim][BF4] solution exists up to around x = 60 mol% H2O, even at T = 77 K.

Fig. 1
Schematic DTA traces of x mol% H2O = (0, 13.0, and 30.1) (from top to the bottom).


Fig. 2
Plot of the of the glass transition temperatures Tg (*) and Tcc (*) as a function of x.
Fig. 3.
The spectral changes of [bmim][BF4]-H2O solutions probed by the Raman CH and OH stretching spectra in the wavenumber region of (2600 to 4000) cm-1 as a function of x. (a) T = 298 K (room temperature), (b) T = 77 K. The peak heights are normalized by the strongest peak of CH stretching vibration of [bmim][BF4]. (from top to the bottom, x mol% H2O = (95.0, 90.0, 80.0, 70.0, 60.0, 50.0, 40.0, 30.0, 20.0, 10.0, 5.0, and 0.0).
Fig. 4.
Spectral changes of the nearly-free hydrogen bonded band (NFHB) in the OH stretching spectra ranging between wavenumber (3300 and 3700) cm-1: (a) T = 298 K (room temperature) and (b) T = 77 K. The peak heights are normalized by the strongest peak of CH stretching vibration of [bmim][BF4] (from top to the bottom, x mol% H2O = (95.0, 90.0, 80.0, 70.0, 60.0, 50.0, 30.0, 15.0, 5.0, and 0.0).
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