From pressure–volume–temperature measurements, in combination with published dielectric spectroscopy results, we assess the volume dependence of structural relaxation in cresolphthalein–dimethylether (KDE). Structural relaxation in KDE cannot be described as either a volume activated or thermally activated process, and unlike results for some other molecular glass formers, temperature is not the dominant control variable. The inflection point of the PVT data yields a glass temperature, Tg, that corresponds to a dielectric relaxation time equal to 10 s. There is a marked variation with pressure, dTg/dP=307 K/GPa at low pressure. We also carried out dynamic mechanical measurements on KDE near Tg. The shape of the mechanical and dielectric relaxation functions, as well as both the magnitude and temperature dependence of the respective relaxation times, are the same. Such equivalence is not generally expected, and arises herein due to the rigid structure of the KDE molecule.

1.
D.
Turnbull
and
M. H.
Cohen
,
J. Chem. Phys.
34
,
120
(
1961
);
D.
Turnbull
and
M. H.
Cohen
,
J. Chem. Phys.
52
,
3038
(
1970
).
2.
M. H.
Cohen
and
G. S.
Grest
,
Phys. Rev. B
20
,
1077
(
1979
).
3.
W.
Götze
and
L.
Sjögren
,
Rep. Prog. Phys.
55
,
241
(
1992
).
4.
T.
Pakula
,
J. Chem. Phys.
94
,
2104
(
1991
).
5.
S. Glasstone, K. Laidler, and H. Eyring, The Theory of Rate Processes (McGraw-Hill, New York, 1941).
6.
J. Frenkel, Kinetic Theory of Liquids (Dover, New York, 1995).
7.
G.
Tarjus
,
D.
Kivelson
, and
P.
Viot
,
J. Phys.: Condens. Matter
12
,
6497
(
2000
).
8.
M. L.
Ferrer
,
C.
Lawrence
,
B. G.
Demirjian
,
D.
Kivelson
,
C.
Alba-Simionesco
, and
G.
Tarjus
,
J. Chem. Phys.
109
,
8010
(
1998
).
9.
W.-X.
Li
and
T.
Keyes
,
J. Chem. Phys.
111
,
328
(
1999
).
10.
M.
Paluch
,
J. Chem. Phys.
115
,
10029
(
2001
).
11.
M.
Paluch
,
K.
Ngai
, and
S.
Hensl-Bielowka
,
J. Chem. Phys.
114
,
10872
(
2001
).
12.
G.
Williams
and
D. C.
Watts
,
Trans. Faraday Soc.
66
,
80
(
1970
).
13.
R.
Böhmer
,
K. L.
Ngai
,
C. A.
Angell
, and
D. J.
Plazek
,
J. Chem. Phys.
99
,
4201
(
1993
).
14.
H.
Sillescu
,
J. Non-Cryst. Solids
243
,
81
(
1998
).
15.
M. T.
Cicerone
and
M. D.
Ediger
,
J. Chem. Phys.
104
,
7210
(
1996
).
16.
C. M.
Roland
,
P. G.
Santangelo
,
D. J.
Plazek
, and
K. M
Bernatz
,
J. Chem. Phys.
111
,
9337
(
1999
).
17.
C. M. Roland and P. G. Santangelo, J. Non-Crystalline Solids (in press).
18.
P. Zoller and D. J. Walsh, Standard Pressure-Volume-Temperature Data for Polymers (Technomic, Lancaster, PA, 1995).
19.
D. W. Van. Krevelsen, Properties of Polymers (Elsevier Science, Amsterdam, 1997).
20.
H.
Schlosser
and
J.
Ferrante
,
J. Phys.: Condens. Matter
1
,
2727
(
1989
).
21.
I.
Avramov
,
J. Non-Cryst. Solids
262
,
258
(
2000
).
22.
I.
Avramov
and
A.
Milchev
,
J. Non-Cryst. Solids
104
,
253
(
1988
).
23.
T.
Atake
and
C. A.
Angell
,
J. Phys. Chem.
83
,
3218
(
1979
).
24.
S. Hensel-Bielowka, J. Ziolo, M. Paluch, and C. M. Roland, J. Chem. Phys. (in press).
25.
E. A.
Dimarzio
,
J. H.
Gibbs
,
P. D.
Fleming
, and
I. C.
Sanchez
,
Macromolecules
9
,
763
(
1976
).
26.
M. Paluch, R. Casalini, S. Hensel-Bielowka, and C. M. Roland, J. Chem. Phys. (in press).
27.
M. Paluch, S. Pawlus, and C. M. Roland (unpublished).
28.
M. Paluch, C. M. Roland, and S. Pawlus, J. Chem. Phys. (in press).
29.
S. P.
Andersson
and
O.
Andersson
,
Macromolecules
31
,
2999
(
1998
).
30.
G.
Fytas
,
A.
Patkowski
,
G.
Meier
, and
Th.
Dorfmuller
,
J. Chem. Phys.
80
,
2214
(
1984
).
31.
G.
Floudas
and
T.
Reisinger
,
J. Chem. Phys.
111
,
5201
(
1999
).
32.
R.
Casalini
,
S.
Capaccioli
,
M.
Lucchesi
,
P. A.
Rolla
, and
S.
Corezzi
,
Phys. Rev. E
63
,
031207
(
2001
).
33.
R.
Casalini
,
S.
Capaccioli
,
M.
Lucchesi
,
P. A.
Rolla
,
M.
Paluch
,
S.
Corezzi
, and
D.
Fioretto
,
Phys. Rev. E
64
,
041504
(
2001
).
34.
G.
Adam
and
J. H.
Gibbs
,
J. Chem. Phys.
43
,
139
(
1965
).
35.
P. G.
Santangelo
and
C. M.
Roland
,
Macromolecules
31
,
3715
(
1998
).
36.
D. J.
Plazek
,
I.-C.
Chay
,
K. L.
Ngai
, and
C. M.
Roland
,
Macromolecules
28
,
6432
(
1995
).
37.
J.
Colmenero
,
A.
Alegria
,
P. G.
Santangelo
,
K. L.
Ngai
, and
C. M.
Roland
,
Macromolecules
27
,
407
(
1994
).
38.
R. Casalini, P. G. Santangelo, and C. M. Roland (unpublished).
39.
N. G. McCrum, B. E. Read, and G. Williams, Anelastic and Dielectric Effects in Polymeric Solids (Dover, New York, 1991).
40.
J.
Colmenero
,
A.
Alegria
,
P. G.
Santangelo
,
K. L.
Ngai
, and
C. M.
Roland
,
Macromolecules
27
,
407
(
1994
).
41.
C. M.
Roland
,
Macromolecules
28
,
3463
(
1995
).
42.
G.
Fytas
,
C. H.
Wang
,
G.
Meier
, and
E. W.
Fischer
,
Macromolecules
18
,
1492
(
1985
).
43.
K. L.
Ngai
,
S.
Mashimo
, and
G.
Fytas
,
Macromolecules
21
,
3030
(
1988
).
44.
A.
Alegria
,
J.
Colmenero
,
K. L.
Ngai
, and
C. M.
Roland
,
Macromolecules
27
,
4486
(
1994
).
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