Room temperature ionic liquids (RTILs) dynamic glass transition

by calorimetric methods.
E. Shoifetab, H. Hutha, S. Verevkinb, and C. Schicka
a

Institute of Physics, Rostock University, Rostock, 18051, Germany

University of Rostock, Institute of Chemistry, 18051 Rostock, Germany

* E-mail:evgeni.shoifet@uni-rostock.de Tel.: +49-381-498-6889Fax: +49-381-498-6889

Many of the ionic liquids are good glass formers [1]. Nevertheless, only a few studies of the
glass transition in ionic liquids are available so far. Particularly the frequency dependence of the
dynamic glass transition (-relaxation) is not known for most ionic liquids. The standard technique
for such studies - dielectric spectroscopy[2, 3] - is not easily applicable to ionic liquids because of
the high electrical conductivity. We try to use calorimetric techniques to obtain complex heat
capacity and to investigate the dynamic glass transition of room temperature ionic liquids (RTILs)
in a wide frequency range. This can give an insight in cooperative motions of ions and ion clusters
in RTILs.
The techniques that were used are DSC, TMDSC[4], and AC-chip calorimeter[5] covering a
frequency range from 0.001 Hz to10000 Hz. RTILs with the same anion show similar fragility. By
varying the cation fragility changes (Figure 1).
Temperature / C
-60

-70

log (max / rad*s^-1 )

-3
4.0

-80

-90

VFT fit parameters:

A = 12,12.6, 9,15
B = 280, 612, 144,647 K
T0 = 192, 140, 171,147.4 K

[C4mim][BF4]
[C2MIM]2[Co(NCS)4])
[C4mim][NTf2]
[C6mim][NTf2]
[C10mim][NTf2]
Blue Ink;Tg(DSC)
[C4MIM][BF4];Tg(DSC)
[C4MIM][NTf2];Tg(DSC)
[C6MIM][NTF2];Tg(DSC)
[C10MIM][NTF2];Tg(DSC)
Fit Curve 1
Fit Curve 1
Fit Curve 1
Fit Curve 1
Fit Curve 1

4.5

2
-6

-4

-2

-2
0

5.0

0
2

-4

4
STRONG

-6

-8

-10

-12
0.0

5.5

-2

[C2MIM]2[Co(NCS)4])
[C4mim][BF4]
[C4mim][NTf2]
[C6mim][NTf2]
[C10mim][NTf2]

8
FRAGILE

log( / rad*s-1)

-50

log ( / sec)

-40

log( \s)

-30

10
12

0.2

1000 K / T

0.4

0.6

0.8

1.0

Tg / T

Figure 1. (left) Relaxation diagram of the glass transition of the studied RTILs. Big rhombic data
points represent the thermal glass transition temperature (DSC, 10 K/min). The solid curves are VFT fits.
(right)Angell plot[6].
Thermal glass transition temperature is increasing with increasing alkyl chain length. That
indicates decreasing mobility. But fragility does not change much.

References
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Karger, F. Kremer, Soft Matter, 7 (2011) 1678-1681.
[3] O. Russina, M. Beiner, C. Pappas, M. Russina, V. Arrighi, T. Unruh, C.L. Mullan, C. Hardacre, A. Triolo,
Journal of Physical Chemistry B, 113 (2009) 8469-8474.
[4] M. Merzlyakov, C. Schick, Thermochim. Acta, 377 (2001) 193-204.
[5] H. Huth, A.A. Minakov, C. Schick, J. Polym. Sci. B Polym. Phys., 44 (2006) 2996-3005.
[6] C.A. Angell, Science, 267 (1995) 1924-1935.