Nonlinear Dielectric Phenomena in Complex Liquids

394 Pages·2005·12.496 MB·English

by  J. -L. Déjardin (auth.), Sylwester J. Rzoska, Vitaly P. Zhelezny (eds.)

Nonlinear Dielectric Phenomena in Complex
Liquids
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Series II: Mathematics, Physics and Chemistry – Vol. 157
Nonlinear Dielectric Phenomena in
Complex Liquids
edited by
Sylwester J. Rzoska
Department of Biophysics and Molecular Physics,
Institute of Physics,
Silesian University, Katowice, Poland
and
Vitaly P. Zhelezny
OdessaState Academy of Refrigeration,
Odessa, Ukraine
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TABLE OF CONTENTS
Introduction ix
Photograph of participants xii
List of participants xiii
Part I: Basics for nonlinear dielectric and related studies in liquids
Anomalous expressions for the nonlinear harmonic components 1
of the electric polarization.
J.-L. Déjardin
Theory of anomalous dielectric relaxation 19
W. T. Coffey
Rotational brownian motion and nonlinear dielectric relaxation of 31
asymmetric top molecules in strong electric fields:
the langevin equation approach
Yu. P. Kalmykov
Experimental solutions for nonlinear dielectric studies in complex liquids 45
M. Górny and S. J. Rzoska
Comments on nonlinear dielectric effect measurements in liquids 55
S. J. Rzoska and A. Drozd-Rzoska
Effect of constraints on electrostriction 57
C. M. Roland and J. T. Garrett
Douglas Kell comments on ‘methodology’ during the workshop 61
D. B. Kell
A new technique of dielectric characterization of liquids 63
N. T. Cherpak, A. A. Barannik, Yu. V. Prokopenko,
T.A. Smirnova, and Yu.F. Filipov
v
vi
Nonlinear dielectric losses and dynamics of intrinsic conductivity 77
of dielectrics
Part II: Nonlinear dielectric and related problems in critical liquids
Dielectric properties of critical conducting mixtures 89
K. Orzechowski, M. Kosmowska
Nonlinear dielectric effect behavior in a critical 101
and near-critical binary mixture.
A. Drozd-Rzoska
Electric fieldeffects near critical points 113
A. Onuki
Critical phenomena in confined binary liquid mixtures 143
A.V. Chalyi, K. A. Chalyi, L. M. Chernenko and A. N. Vasil’ev
Model of the critical behavior of real systems 153
D. Yu. Ivanov
The methods of prediction of the properties for substances on the 163
coexistence curve including vicinity of the critical point.
Vitaly P. Zhelezny
Phase equilibrium in complex liquids under negative pressure 177
A. R. Imre, A Drozd-Rzoska, T. Kraska, K Martinás,
L. P. N. Rebelo, S. J. Rzoska, Z. P. Visak and L. V. Yelash
New approaches to the investigation of the metastable 191
and reacting fluids
P. V. Skripow, S.E. Puchinskis, A.A. Starostin, D. V. Volosnikov
Part III: Nonlinear dielectric results for liquid crystalline materials
The discontinuity of the isotropic – mesophase transition 201
in n-cyanobiphenyls homologous series from 4CB to 14CB.
Nonlinear dielectric effect (NDE) studies.
A. Drozd-Rzoska
Influence of pressure on the dielectric properties of liquid crystals 211
S. Urban and A.
vii
Frequency(cid:1)domain nonlinear dielectric 221
relaxation spectroscopy
Y. Kimura
Phase behavior of perturbed liquid crystals 231
S. Kralj, Z. Kutnjak, G. Lahajnar, M. Svetec
Edge dislocations in smectic(cid:1)a liquid crystals 241
M. Ambrožič , M. Slavinec, S. Kralj
Part IV: Nonlinear dielectric and related studies
for supercooled/superpressed and polymeric liquids
A schematic description of the dynamics of glass transition 247
by the coupling model
K. L. Ngai
Transient grating experiments in supercooled liquids. 259
A. Taschin, M. Ricci, R. Torre, A. Azzimani, C. Dreyfus and R. M. Pick
Medium(cid:1)range ordering in liquids appearing 269
in nonlinear dielectric effect studies
J. Zio(cid:2)o, S. J. Rzoska, A. Drozd(cid:3)Rzoska,
The cooperative molecular dynamics and nonlinear phenomena 275
C. A. Solunov
Annihilation response of ortho (cid:1) positronium probe from positron 289
annihilation lifetime spectroscopy and its relationships
to the free volume and dynamics of glass (cid:1) forming systems
J. Bartoš, O. Šauša, J. Krištiak
Influence of molecular structure on dynamics of secondary 307
relaxation in phthalates,
S. Hensel(cid:3)Bielowka, M. Sekula, S. Pawlus, T. Psurek and Marian Paluch
Electrostriction and crystalline phase transformations 319
in a vinylidene flouride terpolymer
C. M. Roland, J.T. Garrett and S. B. Qadri
viii
Part V: Nonlinear dielectric studies for biologically
and environment relevant materials
Self-assembly and the associated dynamics in 327
PBLG-PEG-PBLGtriblock copolymers
P. Papadopoulos and G. Floudas
Nonlinear dielectric spectroscopy of biological systems: 335
principles and applications
D. B. Kell, A. M. Woodward, E. A. Davies, R. W. Todd, M. F. Evans and Jem J.
Rowland
Measurement method of electric birefringence spectrum 345
in frequency domain,
T. Shimomura, Y. Kimura, K. Ito and R. Hayakawa
Melting/freezing in narrow pores; dielectric and EPR studies 357
G. Dudziak,
R. Radhakrishnan, F. Hung, K.E.Gubbins
Electrodilatometry of liquids, binary liquids, and surfactants 367
M. Rappon, R. M.Johns, and Shih-Wei (Erwin) Lin
Influence of strong electric field on dielectric permittivity 379
of polycrystalline ice doped by small amounts of NAOH
A. Szala, K. Orzechowski
interaction in ACF: EPR study 387
ix
INTRODUCTION
In the last decade the new physics of complex liquids, associated with the search for
universal patterns in such distinct systems as liquid crystals, polymer solutions, critical
mixtures, bio-liquids etc, has emerged. Self-assembling, dominant role of mesoscale
structures, complex dynamics, unusual phases and enormous sensitivity to perturbations
are among the significant features of complex liquids. Extending the definition
proposed by F. Yonezawa et al.[The Physics of Complex Liquids, World. Sci. Pub.,
Singapore, 1998], complex liquids may be classified into the followingcategories:
1 Complex liquids whose complexity originates from specific external conditions, for
instance:
a. “High density liquids ”, such as liquids under high pressure or supercooled
b. “Low density liquids”, such as liquids under negative pressure (stretched
liquids), liquids in a random surrounding (pores etc,..) or in the form of
scattered clusters.
c.Liquids under anisotropic external field, such as liquids under strong electric
field or under shear flow.
d.Liquids near a critical point, including spinodal, multicritical, etc. points.
2. Complex liquids whose complexity is associated with their structure, such as liquid
crystals, polymeric liquids, bio-liquids, micellar solutions, etc..
A rich set of fluid mesophases associated with continuous or weakly discontinuous
phase transitions is also a common feature of complex liquids. Hence, it may be
expected that their properties are dominated by critical-like, pretransitional phenomena.
Surprisingly, the application of the modern physics of critical phenomena may be
puzzling. For instance, in the majority of monographs on the physics of liquid crystals
the isotropic–nematic transition is presented as the best example of a simple mean-field
description. However, recent studies point to a tricritical, “fluidlike” behavior associated
with “glassy” dynamics. It is noteworthy, that the “glassy” dynamics, which is the basic
feature of supercooled liquids is one of the most challenging fields in modern materials
science. One may expect that the “glassy” dynamics may appear as model description
for the whole category of complex liquids. In the last decades, an essentially new
insight into the properties of complex liquids was possible due to the technical progress
in broadband dielectric spectroscopy (BDS). The unique feature of BDS is associated
with the possibility of testing relaxation processes extending in an extraordinary time-
scale range. Nowadays, BDS seems to have reached technical maturity. However,
understanding properties of complex liquids remains far behind. It remains puzzling
even for liquids so extensively studied as the supercooled ones. Hence, the application
of novel research methods may be essential for progress in this field. Since mesoscale,
bond-ordering structures are an inherent feature of complex liquids, research methods
directly coupled to them seem to be of particular importance. One may include here the
transient grating Kerr effect, dynamic light scattering, nonlinear dielectric effect,
dielectric hole-burning spectroscopy and the novel state-of-the-art analysis of broad
band dielectric spectra. An example worth stressing is the nonlinear dielectric effect
x
(NDE), which may be treated as a natural extension of the BDS. NDE describes changes
of dielectric permittivity due to the application of a strong electric field:
where are dielectric permittivities in strong and weak electric field E,
respectively. is the experimental measure of the non(cid:1)linearity called
nonlinear dielectric effect (NDE).
The relevant history of NDE began 80 years ago when Arkadiusz Piekara, at that time a
school teacher in Poland, conducted the first ever measurement of static dielectric
permittivity and NDE near the critical point in nitrobenzene (cid:1) hexane mixture [A.
Piekara, 1932, Phys. Rev. 42, 445(cid:1)447 and A. Piekara, 1936, C. R. Acad. Sci. Paris,
203, pp. 1058(cid:1)1059]. For NDE he noted “a very strong increase on approaching the
critical consolute point” in the homogeneous phase. The explanation of this
phenomenon was not possible until the nineties, when the physics of critical phenomena
and the quasi(cid:1)nematic ordering induced in the mixture by a strong electric field were
taken into account [S. J. Rzoska et al.: Phys. Rev. E 50 (1993)]. At present there are
several experimental techniques applied for NDE measurements. They give insight into
the properties of critical binary liquids and homogeneous liquid crystals (Polish groups),
polymeric films and ferroelectric liquid crystals (Japanese groups) and bio(cid:1)liquids (UK
groups).
The main aim of the ARW NATO “Nonlinear dielectric phenomena in
complex liquids” 10(cid:1)14 May 2003, held in Katowice(cid:1)Jaszowiec (Poland), was the first
ever discussion(cid:1)meeting of researchers interested in nonlinear dielectric phenomena in
complex liquids. Particular attention was paid to the nonlinear dielectric spectroscopy
(NDE). Its limited use so far is related to enormous technical problems encountered.
Therefore the workshop was particularly well timed due to just emerging possibilities of
constructing the first ever, user(cid:1)friendly, nonlinear dielectric spectrometer, giving
insight into time(cid:1)scales relevant for complex liquids. Researchers from almost all
existing groups associated with the nonlinear dielectric spectroscopy and its related
methods took part in the meeting. Discussions were focused on the following items:
1. Basics for nonlinear dielectric and related studies in liquids
2. Nonlinear dielectric and related problems in critical liquids
3. Nonlinear dielectric results for liquid crystalline (mesogenic) materials
4. Nonlinear dielectric and related studies for supercooled/superpressed and
polymeric liquids
5. Nonlinear dielectric studies for biologically relevant materials
The workshop was organized in Jaszowiec Valley, in Hotel Jaskó(cid:2)ka located in the heart
of the Beskidy mountains, 80 km from Katowice, the capital of Upper Silesia, Poland.
Lectures started at 9 am and finished at 6 pm, each lasting 35 minutes, with 45 minute
coffee(cid:1)breaks and party(cid:1)meetings to boost discussions were held every evening.
Participants had also the possibility to get acquainted with the still vivid culture of the
Beskidy highlanders.
This meeting would not have been such a success without the time devoted to its
organization by a number of dedicated people. I would especially like to thank my wife