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Citation: The Journal of Chemical Physics 128, 084511 (2008); doi: 10.1063/1.2834203
View online: http://dx.doi.org/10.1063/1.2834203
View Table of Contents: http://aip.scitation.org/toc/jcp/128/8
Published by the American Institute of Physics
THE JOURNAL OF CHEMICAL PHYSICS 128, 084511 2008
The pressure dependence of the prototypical glass-former propylene carbonate has been investigated
over a broad range of temperature and pressure that were inaccessible in previous investigations
using dielectric spectroscopy. We find that the viscosity measurements validate the scaling relation,
T , V = ITV, with a scaling parameter close to that found from dielectric relaxation
measurements. In the pressure dependence of the viscosity, we observe an inflection point in the
log versus P response, similar to that found previously for other materials. However, this
inflection has never been observed in dielectric relaxation measurements. Using the scaling property
above, it is possible to determine the behavior of the dielectric relaxation time in this otherwise
inaccessible experimental range and compare it with the viscosity measurements. We find that the
behaviors of and are very similar, and a very good agreement between the function P
calculated for these two quantities is found. Starting from the validity of the scaling properties, we
show that the inflection point in the pressure dependence of the viscosity can be attributed to the
convolution of the pressure dependences of the compressibility T and the apparent activation
energy at constant volume EV. 2008 American Institute of Physics. DOI: 10.1063/1.2834203
indicating that the nature of this crossover is not related to a
D TT 0 characteristic temperature or volume.
T = 0 exp , 1
T T0 Here, we investigate the viscosity of a well known glass
former, propylene carbonate14,22 PC under high pressure in
where DT is a constant, T0 is the Vogel temperature at which the regime of low viscosity, where for isobaric processes
should diverge, and 0 is the viscosity in the limit of high there is observed to be a crossover between Arrhenius and
VF behavior. We investigate whether such a crossover can be
a
Electronic mail: casalini@nrl.navy.mil. observed under high pressure in the same manner that the
FIG. 3. Color online Viscosity of PC as a function of the specific volume. FIG. 4. Color online Viscosity of PC vs the function of temperature and
The data at atmospheric pressure are from Refs. 37 and 38 and the specific specific volume, 1000/ TV. The parameter = 4.3 was found empirically to
volume is calculated using the equation of state parameters reported in Ref. give the best superposition. The data at atmospheric pressure are from Refs.
22. Note that the data from Ref. 38 extend to much higher viscosity 37 and 38 and the specific volume is calculated using the equation of state
1012 mPa s but in this figure only the viscosity data close to that of the parameters reported in Ref. 22. Note that the data from Ref. 38 extends to
high pressure measurements are reported. much higher viscosity 1012 mPa s but in this figure only the viscosity data
close to that of the high pressure measurements are reported.
T, P = T,0exp DPP
P0 P
, 4
is not possible since there are no relaxation time data at short
times available. However, as shown before20 using Eq. 2, it M N
P = 0 exp + 5
is possible to determine the behavior of at high pressure P P P P
using the data at atmospheric pressure which are in a more
extended dynamic range, making the comparison between where 0, M, N, P, and P are constants all larger than
and possible. zero and P is a constant less than zero. Using Eq. 5 it is
In the inset of Fig. 6, the data at high pressure are possible to give an accurate description of the behavior of
shown at the temperature corresponding to the measure- at low pressures around the inflection point. This relation has
ments reported in Fig. 1. These data were determined from been useful in tribological calculations of elastohydrody-
the data at atmospheric pressure using Eq. 2 with the namic friction.29 Calculating the function P for the addi-
tional term at low pressure yields a linear function of P like
the JW equation but with a positive linear coefficient, so that
P of Eq. 5 has a maximum at low pressures. However, no
physical meaning was given to this additional singularity at
P.
An understanding of the behavior of the viscosity at low
pressure can be found by starting from Eqs. 2 and 3 to-
gether with the equation from Naoki et al.43
EV
EP
=1
P
T
V
T
P
6
=
1 EP P
PTT EV T
V
T
P
7
ation time open symbols and viscosity data solid symbols. The relaxation
time data were determined from the atmospheric pressure data using Eq. 1 1 T EP
together with the known EOS. The solid lines are the best linear fit, and the = . 8
arrows indicate the crossover B. In the inset are reported the dielectric re- TT P EV
laxation time data for which P is calculated in the main figure same
symbols as in the main figure. Finally, using the property of the derivatives,
084511-5 Temperature and pressure dependence of PC viscosity J. Chem. Phys. 128, 084511 2008
rithm of the viscosity divided by the temperature vs the logarithm of the
T T dielectric relaxation time. The lines are linear fit, the linear coefficients are
= , reported in the figure. Top inset: logarithm of the viscosity divided by the
P P T P temperature and the dielectric relaxation time vs the inverse temperature.
The lines are the same fit reported in the main figure.
and the definitions of E P and V given above, it follows that
1 V curve. To better show the superposition of the high pressure
= . 9 data, we report the data in more detail in Fig. 9, since the
T EV
high pressure data are in a more limited dynamic range.
Therefore, since is constant, the pressure dependence of From the analysis of the data, we find that the linear coeffi-
the activation volume is given by the product of EV and T. cient is very close to 1 only in the range between the cross-
In Fig. 7 we show T and EV versus pressure, where EV was over B and the glass transition, while above the crossover B
calculated using the scaling property Eq. 2 as B, B the coefficient is 1.25 0.01. To show this
EV = RT1 log / log V. As shown in Fig. 7, EV mono- we also reported in the top inset of Fig. 8 the quantity
tonically increases with pressure, while T monotonically de- logT11 versus the inverse temperature. The product
creases with pressure and the convolution of these two op- T11 increases with decreasing temperature, similarly to
posite behaviors gives rise to the minimum in the behavior of what was observed for other glass formers.11 At high tem-
V shown in Fig. 2 and also to the maximum in the function perature, logT11 8.2, while at low temperature close
P in Fig. 6. to Tg, logT11 9.3. According to Eq. 10 it is possible
Thus, the inflection point in the pressure behavior of the
viscosity is mainly due to the higher compressibility of the
liquids at low pressure; however, this is more evident at high
temperatures T TA where EV tends to be less pressure
dependent. This effect is also probably the reason why, dif-
ferently from the crossover B, the crossover A is not evident
in isothermal measurements of relaxation time.
The behavior of the viscosity and the dielectric relax-
ation time at different conditions of temperature and pressure
according to the StokesEinsteinDebye SED
relationship11 should satisfy
k BT
= 4rH
3
, 10
where kB is the Boltzmann constant and rH is the hydrody-
namic radius of the diffusing molecule assumed to have
spherical shape. To verify Eq. 10, we report in Fig. 8 the
logarithm of the ratio / T versus the logarithm of , which
according to SED, assuming rH is the same for different dy-
FIG. 9. Color online Check of the DebyeStokes relation. Detail of Fig. 8
namic conditions, should have a linear coefficient equal to 1.
showing the high pressure data. Logarithm of the viscosity divided by the
We find that all the data at different conditions of tem- temperature vs the logarithm of the dielectric relaxation time. The line is a
perature and pressure superimpose onto a single master linear fit and the coefficient is reported in the figure.
084511-6 R. Casalini and S. Bair J. Chem. Phys. 128, 084511 2008
to estimate the hydrodynamic radius rH. We find that in the efficient between logT1 and log is 1.25 0.01 instead
limit of high temperature T TA rH = 0.19 nm, from which of unity as predicted by Eq. 10, and it is independent of
assuming a spherical form for the molecule we calculated pressure. Moreover, the estimated hydrodynamic radius rH is
VH = 17.8 cm3 mol1. We observe that the value of VH is re- of the same order of magnitude of the van der Waals radius
markably close to the value of the activation volume V. rVW as found for other glass formers,11 and that in the region
Taking the data in the literature of salol and orthoterphenyl above the crossover A, the hydrodynamic volume assuming
OTP,11,53 we find V1.5Tg = 25 1 cm3 mol1 and VH a spherical form of the molecule is quite close to the acti-
= 27 cm3 mol1 for salol and V1.6Tg = 33 2 cm3 mol1 vation volume for PC. This was found to be valid also for
and VH = 31 cm3 mol1 for OTP; therefore, the fact, that for OTP and salol.
PC, V and VH have similar values may not be fortuitous,
however further investigations are necessary to understand ACKNOWLEDGMENTS
the generality of this observation. A comparison found in the
literature is that between VH and the van der Waals volume The work at Naval Research Laboratory was supported
VVW calculated as discussed in Refs. 54 and 55. For PC we by the Office of Naval Research.
calculated VVW = 44.7 cm3 mol1, therefore, rVW 1.4rH,
1
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