6404 Langmuir 2002, 18, 6404-6409

Dielectric Relaxations in Aqueous Polyelectrolyte

Solutions: A Scaling Approach and the Role of the Solvent
Quality Parameter
F. Bordi
Dipartimento di Medicina Interna, Università di Roma “Tor Vergata”, Rome, Italy, and
Istituto Nazionale per la Fisica della Materia (INFM), Unita’ di Roma1

C. Cametti* and T. Gili

Dipartimento di Fisica, Università di Roma “La Sapienza”, Piazzale A. Moro 5-I-00185 Rome,
Italy, and Istituto Nazionale per la Fisica della Materia (INFM), Unita’ di Roma1

R. H. Colby
Department of Materials Science and Engineering, The Pennsylvania State University,
University Park, Pennsylvania 16802

Received February 19, 2002. In Final Form: April 25, 2002

The radiowave dielectric behavior of sodium polyacrylate (NaPAA) aqueous solutions, in an extended
concentration range and at various degrees of polymerization, was analyzed in the light of the scaling
approach for polyelectrolyte solutions recently proposed by Dobrynin et al. [Macromolecules 1995, 28,
1859]. In the frequency range from 1 MHz to 1 GHz, the observed dielectric relaxation is attributed to the
fluctuation of loosely bound counterions over a characteristic correlation length which depends on the
polymer concentration. Assuming that free counterions fluctuate on a length scale that is proportional to
the correlation length ξ0 of the semidilute solution, we derived power laws for the dielectric strength ∆
and the relaxation frequency ν0. In agreement with our recently published data on conductivity, the dielectric
data indicate that the effective charge on the NaPAA chains increases as concentration is raised, until
the correlation length reaches the size of the electrostatic blob. By comparing the dielectric behavior of
a series of polymers exhibiting different affinities for water as a solvent, we showed that the scaling
behavior furnishes a very good description of the observed concentration dependence of the dielectric
parameters. These findings suggest a method for evaluating, from simple dielectric measurements, the
solvent quality parameter τ for the uncharged polyelectrolyte chain, a parameter which up to now eluded
a precise determination by means of other experimental techniques. Finally, a correlation between the
fraction f of free counterions and the solvent quality parameter τ, in poor solvent conditions, was evidenced.
This gives further support to the hypothesis that the effective polyelectrolyte-solvent entropic interaction
is primarily dictated by the effective charge on the chain.

1. Introduction region, the mechanism causing the dispersion has been

The dielectric behavior of aqueous polyelectrolyte solu-
tions has been extensively investigated in the past few
decades,1-7 and a common picture has been now estab-
lished, consisting, at least, of the presence of three
different, partially overlapping, relaxation regions, rang-
ing from some hertz to microwave frequencies. This
complex phenomenology is attributed to different molec-
ular level mechanisms, originated or induced by the
external electric field. Whereas in the low-frequency and
in the high-frequency regions the observed dielectric
dispersions are characterized by length scales related to
the polymer chain size and to that of the solvent phase
molecules, respectively, in the intermediate-frequency
* To whom correspondence should be addressed.
(1) Polyelectrolytes: Science and Technologies; Hara, M., Ed.; Marcel
Dekker: New York, 1993.
(2) Oosawa, F. Polyelectrolytes; Marcel Dekker: New York, 1970.
(3) Schmitz, K. S. Macroions in solution and colloidal suspensions;
VCH: New York, 1993.
(4) Mandel, M. In Polyelectrolytes: Science and Technologies; Hara,
M., Ed.; Marcel Dekker: 1993.
(5) Bordi, F.; Cametti, C.; Paradossi, G. Biopolymers 1995, 36, 539.
(6) Bordi, F.; Cametti, C.; Paradossi, G. Biopolymers 2000, 53, 129.
(7) Bordi, F.; Cametti, C.; Motta, A. Macromolecules 2000, 33, 1910.
for a long time more controversial and only recently has
been attributed to local fluctuation of counterions along
some typical correlation length.8,9
Although various theoretical approaches have been
developed, most of them neglect polyion-polyion interac-
tion as well as the influence of the solvent on the polyion
chain conformation.
The scaling theory of polyelectrolyte solutions,10,11 based
on the idea of de Gennes et al.12,13 of electrostatic blobs
inside which Coulombic repulsion competes with polymer-
solvent interactions to determine the chain configuration,
provides a description of the overall chain conformation
in the different concentration regimes, which can be
summarized as follows. When the electrostatic screening
(8) Ito, K.; Yagi, A.; Ookubo, N.; Hayakawa, R. Macromolecules 1990,
23, 857.
(9) Odijk, T. Macromolecules 1979, 12, 688.
(10) Rubinstein, M.; Colby, R. H.; Dobrynin, A. V. Phys. Rev. Lett.
1994, 73, 2776.
(11) Dobrynin, A. V.; Colby, R. H.; Rubinstein, M. Macromolecules
1995, 28, 1859.
(12) de Gennes, P. G.; Pincus, P.; Velasco, R. M.; Brochard, F. J.
Phys. France 1976, 37, 1461.
(13) de Gennes, P. G. Scaling Concepts in Polymer Physics; Cornell
University Press: Ithaca, NY, 1980.

10.1021/la020175h CCC: $22.00 © 2002 American Chemical Society

Published on Web 07/13/2002
Dielectric Relaxation in Polyelectrolyte Solutions
length rs is much larger than the electrostatic blob size
D, Coulomb repulsion stretches the chain into a quite stiff
cylinder. With the increase of the polymer concentration,
when the screening length becomes smaller than the
extended chain size, on length scales of the order of rs the
chain is still a rodlike sequence of electrostatic blobs. On
longer length scales, however, the chain is a random walk,
where the screening length plays the role of a correlation
length ξ0.
In salt-free solutions, the concentration where rs
becomes approximately equal to the length of a fully
extended chain of electrostatic blobs, L, is in the same
concentration range of the overlap concentration c*, when
the distance between chains is equal to their extended
size L. As a consequence, while for c < c* the polymer
solution is in the dilute regime, for c* < c < ce the solution
consists of space-filling correlation blobs of size ξ0 ≈ rs
(semidilute-unentangled regime). As the concentration
is further increased, a concentration ce is reached where
a significant overlap of neighboring chains is attained
and they begin to constrain each other (semidilute-
entangled regime). Finally, above the concentration cD,
electrostatic blobs overlap, and the chain configuration is
expected to cross over to that of uncharged polymer.
In the present work, we have analyzed the radiowave
dielectric properties of sodium polyacrylate aqueous
solutions in a wide concentration range, from the dilute
to the concentrated regime, in particular from the
crossover between dilute and semidilute-unentangled to
semidilute-entangled and concentrated regimes. Within
these concentration regimes, the polyion chain assumes
different configurations, causing a different dielectric
behavior observed in the intermediate relaxation process.
From the dielectric relaxation point of view, the model
of Ito et al.8 assumes that the observed intermediate
relaxation is due to counterion fluctuations on a length
scale that depends on polyelectrolyte concentration. In
dilute solutions, the chains are very far apart and can be
considered as pointlike charges in the center of a spherical
cell. In this case, the “fluctuation length” is proportional
to the cell diameter and scales as c-1/3. At higher
concentrations, when the distance between the chains
becomes comparable with their length, the cylindrical cell
model applies and the fluctuation length scales as c-1/2.
Along this scheme, we assume that in the semidilute
regime, counterions might fluctuate on a length scale that
is proportional to the correlation length ξ0 defined within
the scaling theory of polyelectrolyte solutions,10,11 and we
derive the power-law dependencies for the dielectric
parameters in the semidilute regime, according to the
different solvent quality.
In this paper, we analyze the dielectric behavior of
polyelectrolyte aqueous solutions in light of the scaling
approach for polyelectrolyte solutions in good solvent
conditions. Moreover, within the same scheme we have
reanalyzed the dielectric behavior of a series of different
polymers with different hydrophobicities, the water phase
behaving, in this case, as a poor solvent. Also in this case,
we will show that the scaling behavior furnishes a very
good description of the observed concentration dependence
of the dielectric parameters. These findings allow us to
suggest a method for evaluating, from rather simple
dielectric measurements, the solvent quality parameter
τ for the chain, a parameter which is difficult to estimate
experimentally by means of other techniques. Finally, the
correlation between the free counterion fraction f and the
solvent quality parameter τ is discussed. This gives further
support to the hypothesis that the effective polymer-
Langmuir, Vol. 18, No. 16, 2002 6405
solvent energetic interaction is primarily dictated by the
effective charge on the polyelectrolyte chain.
2. Experimental Section
The dielectric spectrum of sodium polyacrylate aqueous
suspensions has been measured in the frequency range from 1
MHz to 1.8 GHz where a well-defined dielectric dispersion due
to counterion fluctuation along the characteristic correlation
length ξ0 occurs.
Six samples of sodium polyacrylate with nominal molecular
weights of 2.1, 5.1, 20, 60, 140, and 225 kD were purchased from
Polysciences Inc., Warrington, PA, as 20 or 25 wt % solutions in
water and were used without any further purification. The
polymers have a moderate polydispersity with a weight-averaged
to number-averaged molecular weight Mw/Mn < 1.2 for all the
samples investigated. The pH values of the solutions, for all the
molecular weights investigated, show a continuous moderate
decrease as the polymer concentration is increased, varying from
about pH ) 9.0 at C ) 0.01 g/mL to about pH ) 8.0 at C ) 0.2
g/mL. At these pH values, the polymer behaves as a polyelec-
trolyte.
Polymer solutions at the desired concentrations in the range
from 0.001 to about 0.5 wt/wt were prepared with Q-quality water
(Millipore) with an electrical conductivity at room temperature
of 1-2 µΩ-1 cm-1. The polymer concentration investigated
covers the dilute to concentrated regime, crossing the different
crossovers between semidilute-unentangled, semidilute-en-
tangled, and concentrated regimes.
The dielectric spectra have been measured by means of a radio
frequency impedance analyzer, Hewlett-Pachard model 4291A,
at the temperature of 20 °C. Details of the dielectric cell and the
calibration procedure have been reported elsewhere.14,15
3. Scaling of the Dielectric Parameters
The polyelectrolyte solution contains Np flexible charged
polyions per unit volume, each of them built up of N
monomers of size b carrying an ionizable group of charge
zpe and a counterion of charge z1e, where zp and z1 are
their valences, respectively, and e is the electronic charge.
Owing to the counterion condensation, an effective charge
per polyion will appear, Q ) fNe, where f is the fraction
of ionized groups (or conversely, of free counterions, after
condensation takes place).
In the semidilute regime (c > c*), when electrostatic
and excluded volume interactions are screened on a length
scale larger than the correlation length, each chain is
represented by a random walk of Nξ0 ) N/g correlation
blobs of size ξ0, containing an electric charge qξ0 ) fge,
where g is the number of monomers inside a correlation
blob.
The dielectric relaxation, intermediate between that
where the polarization due to the whole polyion length
dominates and that where the relaxation of the pure water
occurs, results from the counterion polarization on a length
scale of the order of the correlation length ξ0. According
to Ito et al.,8 this process causes a dielectric strength ∆
and a relaxation frequency ν0 given by
∆ ≈ fclBwξ02 (1)
D
ν0 ≈ (2)
ξ02
respectively, where lB ) e2/wkBT is the Bjerrum length
and w is the permittivity of the aqueous phase. Here, D
is the diffusion coefficient of free counterions, which we
take to be identical to that of the counterion in a dilute
(14) Takashima, S.; Casaleggio, A.; Giuliano, F.; Morando, M.; Arrigo,
P.; Ridella, S. Biophys. J. 1986, 49, 1003.
(15) Bordi, F.; Cametti, C.; Paradossi, G. Biopolymers 1996, 40, 485.
6406 Langmuir, Vol. 18, No. 16, 2002
simple salt solution, and kBT is the thermal energy.
Combining eqs 1 and 2 to eliminate ξ0 gives
ν0∆
f≈ (3)
DclBw
which allows the fraction of free counterions to be
determined from the measurement of the intermediate
frequency dielectric relaxation alone, independently of the
solvent quality.
Moreover, eq 2 links the relaxation frequency ν0 to the
correlation length ξ0, which, in turn, depends on the
polyion chain configuration and on its specific electrostatic
interaction with the solvent. Following the scaling ap-
{
proach proposed by Dobrynin et al.,10,11 the correlation
length ξ0 is given by
τ1/2
T<θ
f 2/3lB1/3b1/6c1/2
1 parameters (∆ and ν0) provide a simple means to estimate
ξ0 ≈ 1/3 1/6 1/3 1/2 T ) θ (4)
f lB b c
1
T>θ
f 2/7lB1/7b5/14c1/2
where τ ) (θ - T)/θ is the solvent quality parameter and
θ is the temperature at which the net excluded volume for
the monomer is zero. Their dependence on the polymer
concentration c provides a simple means to estimate the
solvent quality parameter, its influence on the dielectric
parameters, and, more generally, the interaction with the
solvent.
Combining eqs 1 and 4 to eliminate ξ0 and substituting
the expression for f given by eq 3 results in the following
power-law dependencies:
τ-1ν01/3∆4/3 ≈ c1/3 (5)
in the case of poor solvent, T < θ,
ν0-1∆2 ≈ c-1 (6)
in the case of a θ solvent, T ) θ, and finally
ν0-1∆4/3 ≈ c-1 (7)
in the case of good solvent, T > θ. Whereas eqs 6 and 7
clearly indicate a dependence on the polymer concentration
as c-1, in the case of poor solvent, the dependence is less
obvious owing to the presence of the further parameter
τ which in turn varies with the concentration c.
On the other hand, in the case of poor solvent, if
expressions 1 and 2 for dielectric parameters ∆ and ν0
are conveniently rearranged and the appropriate depen-
dence for ξ0 (T < θ) (eq 4) is taken into account, a
relationship between τ and f can be easily obtained in the
form
()
fb 1/3∆
τ) (8)
lB w
suggesting that there may be some correlation between
the solvent quality factor and the fraction f of free
counterions, for a polyelectrolyte in a poor solvent.
A further comment is in order. Ito et al.8 have dem-
onstrated that for a polyelectrolyte solution in a given
solvent, in the semidilute regime, ∆ is proportional to
the concentration c, to the fraction f of free counterions,
Bordi et al.
and to the square of the correlation length ξ0, while the
relaxation frequency ν0 is proportional to the inverse of
ξ02 (eqs 1 and 2). On the other hand, the dependence of
ξ0 on the concentration c predicted by de Gennes12 (eq 4)
has been confirmed for different polyelectrolytes by small-
angle neutron scattering experiments.16,17 With this
dependence, eq 2 predicts a relaxation frequency that
increases with concentration as c and, if the fraction f of
free counterions is independent of concentration, a
constant value of ∆ should be obtained (eq 1). This
expected behavior has been actually experimentally
verified for NaPSS in the concentration range from 10-4
to 10-1 monomol/L.8 However, when the concentration is
sufficiently high, these dependencies are no longer true,
and while eq 2 still describes the concentration dependence
of ν0, the dielectric increment shows a significant increase,
reflecting a dependence of the fraction f of free counterions
on the polymer concentration. The polymer investigated
in this work clearly evidences this behavior in the
semidilute regime (see data analysis, Figure 2). Dielectric
f from exclusively experimental quantities. As a final
remark, it must be noted that for a polymer in a poor
solvent ξ0 depends on c both explicitly and through the
fraction f (eq 4). Since only the expected dependence of ξ0
on c-1/2 is experimentally observed, this implies that the
dependence on f has to be somehow compensated. Actually,
as we have recently demonstrated, in the case of poor
solvent conditions,18 there is a correlation between f and
the solvent quality parameter τ, so that the expected power
law ξ0 ∼ c-1/2 is satisfied.
4. Results and Discussion
4.1. Data Analysis. Representative dielectric spectra
of sodium polyacrylate aqueous solutions of two different
molecular weights (5.1 and 140 kD) at a selected polymer
concentration (C ) 0.7 wt %) are shown in Figure 1. All
the polymers investigated display a well-defined dielectric
dispersion with relaxation times falling in the interval
10-8 to 10-10 s, intermediate between the low-frequency
dispersion associated with motions involving the whole
polymer chain and the high-frequency dispersion due to
the orientational polarization of water.
In the frequency range investigated, the complex
dielectric constant *(ω) has been analyzed on the basis
of the following expression:19
( )
σ0
σ(ω)
*(ω) ) ′(ω) - i ) ′(ω) - i ′′diel + )
0ω 0ω
 - ∞ ∞ - ∞H2O σ0
+ -i (9)
1 + (iωτ) β 1 + iωτH2O 0ω
where ∆ )  - ∞, ν0 ) ω0/2π, and β (the dielectric strength,
relaxation frequency, and relaxation time spread, respec-
tively) are the dielectric parameters of a Cole-Cole
relaxation function, ∆H2O ) ∞ - ∞H2O and ν0H2O ) ω0H2O/
2π are the dielectric parameters (dielectric strength and
relaxation frequency, respectively) of a Debye type re-
laxation function taking into account the contribution from
polarization of water, σ0 is the dc electrical conductivity,
(16) Nierlich, M.; et al. J. Phys. France 1979, 40, 701.
(17) Essafi, W.; Lafuma, F.; Williams, C. E. Eur. Polym. J. B 1999,
9, 261.
(18) Bordi, F.; Cametti, C.; Tan, J. S.; Boris, D. C.; Krause, W. E.;
Plucktaveesak, N.; Colby, R. H. Macromolecules, in press.
(19) Grant, E. H.; Sheppard, R. J.; South, G. P. Dielectric Behaviour
of Biological Molecules in Solutions; Clarendon Press: Oxford, 1978.
Dielectric Relaxation in Polyelectrolyte Solutions
Figure 1. The permittivity ′(ω) (A) and the dielectric loss
′′(ω) (B) of sodium polyacrylate aqueous solutions for two
molecular weights (top curve, MW ) 140 kD; bottom curve,
MW ) 5.1 kD) as a function of frequency. The polymer
concentration is C ) 0.7 wt %. The temperature is T ) 20 °C.
The full lines are the calculated values on the basis of a
simultaneous fitting (the real and imaginary part) of the
relaxation function (eq 9) to the experimental values.
and, finally, 0 is the dielectric constant of free space and
ω is the angular frequency of the applied electric field.
We have assumed that the low-frequency process will
finish at frequencies lower than 1 MHz, so that we can
exclude, in the low-frequency window investigated, any
small contribution from this process. The deconvolution
of a dielectric spectrum covering an extended frequency
range, where different relaxation mechanisms overlap, is
a very difficult task. This difficulty is particularly severe
when the high electrical conductivity of the samples to be
studied gives rise to a frequency-dependent loss process
whose tail falls within the frequency window investigated.
In the present case, with dc electrical conductivities of
the order of 1 Ω-1 m-1, the contribution to the total
(dielectric) loss deriving from the dc conductivity domi-
nates that from the dielectric relaxation process. The term
σ0/0ω is about 2 × 104, whereas we expect a dielectric loss
of the order of ′′ ≈ 10. Moreover, the intrinsic phase angle
φ of the conducting solution defined according to the
following expression (assuming the dielectric loss con-
tribution ′′(ω) to be negligible)
′ν
tan φ ) 2π0 (10)
σ0
at a frequency as high as ν ) 1 MHz is of the order of 0.005
rad, that is, less than 0.3°. These difficulties of a purely
experimental nature make accurate evaluation of the
dielectric parameters quite difficult and make a rather
elaborate analysis necessary.
Langmuir, Vol. 18, No. 16, 2002 6407
Figure 2. The dielectric increment ∆ of sodium polyacrylate
aqueous solutions as a function of the polymer concentration,
for different molecular weights: (O) 225 kD; (0) 140 kD; (]) 60
kD; (4) 20 kD; (3) 5.1 kD; (b) 2.1 kD. The temperature is T )
20 ° C.
As we have previously stated, the deconvolution of the
whole dielectric spectrum into its components in the case
of high-conductivity aqueous solutions is very difficult, in
this case, being further complicated by the fact that due
to the conductivity the experimental resolution is low and
that in our frequency window we can observe only the
high-frequency tail of the dc conductivity losses and only
the low-frequency tail of the polarization of water.
In particular, the localization of the main frequency
relaxation by observing separately the permittivity and
the dielectric loss spectra may be doubtful, thus influencing
the evaluation of the whole set of the dielectric parameters.
To overcome this difficulty, we have performed a multiple-
step fitting procedure based on the Marquardt algorithm
for complex functions.19 Since the shape of the dielectric
loss spectrum ′′ strongly depends on the value of the dc
electrical conductivity σ0 to be subtracted from the total
loss σ(ω)/0ω, we have made a preliminary simultaneous
fit of ′(ω) and the total loss σ(ω)/0ω with five free
parameters ∆, τ, β, ∞, and σ0 with the only constraint
that all parameters should be positive. The value of σ0
thus obtained is then subtracted from the measured
conductivity σ(ω), the dielectric loss ′′(ω) is evaluated,
and a new set of parameters from the simultaneous fit of
both the permittivity ′(ω) and ′(ω) are now obtained.
This procedure is iterated until a reasonable minimization
is reached. We have successfully applied this procedure
to the analysis of the dielectric spectra of poly-L-lysine
aqueous solutions at different polymer concentrations.6,7,20
In the present case, the dielectric parameters character-
izing the intermediate dielectric dispersion determined
by the nonlinear least-squares minimization on the basis
of the modified Cole-Cole relaxation function (eq 9) are
shown in Figures 2-4.
4.2. Scaling Analysis. Here, we discuss the dependence
of the dielectric parameters in light of the scaling approach.
To this end, the polymer concentration regimes we have
investigated must be assessed.
In a previous work,21 we have estimated from viscosity
measurements the different characteristic concentrations
that define the limits of the different concentration regimes
for the sodium polyacrylate aqueous solutions investi-
gated. These values are approximately c* ) 0.0005
monomol/L, ce ) 0.2-0.3 monomol/L, and cD ) 1-2
(20) Bordi, F.; Cametti, C.; Paradossi, G. Phys. Chem. Chem. Phys.
1999, 1, 1555.
(21) Bordi, F.; Colby, R. H.; Cametti, C.; De Lorenzo, L.; Gili, T. J.
Phys. Chem., in press.
6408 Langmuir, Vol. 18, No. 16, 2002
Figure 3. The relaxation frequency ν0 of sodium polyacrylate
aqueous solutions as a function of the polymer concentration,
for different molecular weights: (O) 225 kD; (0) 140 kD; (]) 60
kD; (4) 20 kD; (3) 5.1 kD; (b) 2.1 kD. The temperature is T )
20 °C.
Figure 4. The parameter β of the spread of the relaxation
frequency of sodium polyacrylate aqueous solutions as a function
of the polymer concentration, for different molecular weights:
(O) 225 kD; (0) 140 kD; (]) 60 kD; (4) 20 kD; (3) 5.1 kD; (b)
2.1 kD. The temperature is T ) 20 °C.
monomol/L, corresponding to c* ≈ 10-5 wt/wt, ce ≈ 2-3
× 10-2 wt/wt, and cD ≈ 0.1-0.2 wt/wt, respectively.
On the basis of these values, the polyion solution is in
the semidilute-unentangled regime for c* < c < ce, in the
semidilute-entangled regime for ce < c < cD, and in the
concentrated regime for c > cD, the dilute regime being
well below the lowest concentration investigated.
As can be seen (Figure 2), the dielectric increment ∆,
for the higher molecular weights studied (20, 60, 140, and
225 kD), increases up to c ≈ ce; it remains approximately
constant in the semidilute-entangled regime (ce < c < cD)
and then markedly decreases for c > cD. This finding is
qualitatively in agreement with the model of Ito et al.8
that predicts a dielectric increment independent of
concentration in the semidilute regime and an increasing
behavior at lower concentrations. The lowest molecular
weights (2.1 and 5.1 kD) behave similarly, even if the
semidilute-entangled regime extends over a narrow
interval, shifted toward higher concentrations. As far as
the relaxation frequency is concerned (Figure 3), in the
whole semidilute regime (c* < c < cD), an approximately
linear dependence on c is observed, marked deviations
occurring only at concentrations larger than cD.
In the present case, the fraction f of free counterions,
calculated on the basis of the dielectric parameters ∆
and ν0 (eq 3), does not have a constant value in the whole
concentration range where the system is in the semidilute
regime and the independence of c for the quantity ν0∆/c
is no longer verified.
On the contrary, if eq 7 holds (good solvent conditions),
a very good agreement with the experimental behavior is
Bordi et al.
Figure 5. The scaling behavior of the dielectric parameter ∆
and ν0 as a function of the concentration c for sodium poly-
acrylate aqueous solutions of different molecular weights at
the temperature of 20 °C: (O) 225 kD; (0) 140 kD; (]) 60 kD;
(4) 20 kD; (3) 5.1 kD. The dependence 1/c is that expected for
good solvent conditions.
obtained. Figure 5 shows the dependence of ∆4/3/ν0 on the
concentration c, which displays the slope of -1 as expected.
These findings give strong support to a description of
dielectric relaxation based on the Ito et al. model,8 with
the characteristic distance on which the counterions
fluctuate being the correlation length ξ0 (or proportional
to this length) obtained from the scaling theory of
polyelectrolyte solutions.10,11
On the basis of these findings, the intermediate dielectric
dispersion in highly charged polyelectrolyte solutions and
the consequent extraction of the dielectric strength and
relaxation frequency provide a simple and unique means
to evaluate the interaction of the polyelectrolyte with the
solvent phase through the solvent quality parameter.
Further support for this picture emerges when different
polymers are considered, for which water represents a
“poor” solvent. In our previous work,18 we have analyzed
the intermediate dielectric dispersions of different poly-
mers in aqueous solution in the case of poor solvent
conditions. We investigated four different polymers with
decreasing chain charge density, that is, the sodium salt
of sulfonated polystyrene [NaPSS], the sodium salt of
poly(2-acrylamido-2-methylpropane sulfonate) [NaPAMS],
a random copolymer made from 80% 2-acrylamido-2-
methylpropane sulfonate and 20% acrylamide [NaPAMS/
PA20], and a random copolymer made from 45% 2-acry-
lamido-2-methylpropane sulfonate and 55% tert-butyl-
acrylamide [NaPAMS345/PtBA55], and we have analyzed
the scaling power laws given in eqs 5-7. A plot of ν0-1∆4/3
as a function of 1/c (eq 7) for these four polymers at the
temperature of T ) 20 °C is shown in Figure 6. In this
case, a good solvent condition is clearly inappropriate to
describe the dependence on the concentration c. As can be
seen, deviations from a straight line with a slope of -1
appear well below the concentration cD, suggesting that
eq 7 fails and, owing to the hydrophobicity of the polymers,
a poor solvent condition should be more appropriate.
This trend is further confirmed by the data shown in
Figure 7, where the quantity ∆4/3/ν0 for the same polymer
solutions is shown at a higher temperature (T ) 40 °C).
In this case, the polymer-solvent interactions are favored
and the good solvent conditions are better approached. As
can be seen, deviations from a slope of -1 are less evident
for all the four polymers investigated and eq 7 works over
the whole semidilute concentration regime.
As we have stressed above, eq 5 in the case of a poor
solvent is unable to furnish a well-defined concentration
dependence owing to the dependence of the solvent quality
Dielectric Relaxation in Polyelectrolyte Solutions
Figure 6. The scaling behavior of the dielectric parameter ∆
and ν0 as a function of the concentration c for different poly-
mers at the temperature of 20 °C: (O) NaPAMS45/PtBA55; (0)
NaPSS; (]) NaPAMS; (4) NaPAMS80/PA20. The data are
shifted along the y-axis to have them coincide with the calcu-
lated curve 1/c that is expected for good solvent conditions.
Deviations in the high concentration range indicate that good
solvent conditions are inappropriate.
Figure 7. The scaling behavior of the dielectric parameter ∆
and ν0 as a function of the concentration c for different poly-
mers at the temperature of 40 °C: (O) NaPAMS45/PtBA55;
(0) NaPSS; (]) NaPAMS; (4) NaPAMS80/PA20. The data are
shifted along the y-axis to have them coincide with the calculated
curve 1/c that is expected for good solvent conditions.
parameter τ on c. However, the influence of the solvent
and then the electrostatic interaction with the aqueous
phase can be implicitly derived from eq 8, giving the
dependence of the quality solvent parameter τ on the
fraction f of free counterions. We plot τ as a function of f
in Figure 8 for the four polymers at the temperature of
T ) 20 °C (poor solvent conditions). As can be seen, there
exists a strong correlation and furthermore a logical
progression in both the fraction of monomers bearing a
charge f (and consequently the fraction of free counter-
ions) and the solvent quality parameter τ. As the fraction
f of monomers having salt groups increases from 0.45
(NaPAMS45/PtBA55) to 0.8 (NaPAMS80/PA20) to 1
(NaPAMS and NaPSS), both f and τ steadily increase.
Finally, values of the solvent quality parameter in the
range of 0.05-0.25 compare reasonably well with those
derived assuming a θ-temperature falling in the interval
45-55 °C, according to the different hydrophobicity of the
polymers investigated.
Langmuir, Vol. 18, No. 16, 2002 6409
Figure 8. Correlation between the solvent quality parameter
τ and the fraction of monomers bearing an effective charge (or,
conversely, the fraction of free counterions) f for different
polymers at the temperature of 20°: (O) NaPAMS45/PtBA55;
(0) NaPSS; (]) NaPAMS; (4) NaPAMS80/PA20.
The correlation shown in Figure 8 gives support to the
ansatz that the correct solvent quality parameter in the
scaling theory of polyelectrolyte solutions is not the
energetic interaction between uncharged polymer and the
solvent, but it is completely dwarfed by the interaction
between a bare charge and water.
5. Conclusions
Although dielectric and electrical conductivity proper-
ties of polyelectrolyte solutions have been extensively
studied in highly diluted systems, only a few studies cover
a wide concentration range, from semidilute to concen-
trated regimes. In this paper, we have shown that the
relaxation process occurring at intermediate frequencies
(1 MHz to 1 GHz) due to fluctuation of free counterions,
according to the Ito et al. model,8 can be described within
the scaling theory of polyelectrolyte solutions10,11 that
furnishes a simple and effective description of the observed
dependence of the dielectric parameters on the polymer
concentration in the whole concentration range we have
investigated. Moreover, we have also shown that this
simple scheme allows the quality solvent parameter τ to
be evaluated experimentally in the poor solvent case. This
parameter in the scaling theory of polyelectrolytes takes
into account the interaction between the solvent and the
uncharged chain, that is, the effective interaction with
solvent that the chain would exhibit if it were uncharged.
This particular aspect of τ makes it difficult to measure
this parameter, because the chain is, in effect, charged.
The fact that dielectric parameters, for polymers that have
a different affinity for water, show a different scaling
behavior, in agreement with the known hydrophobicity of
the chain, gives strong experimental support to the scaling
approach. The observed correlation between the fraction
f of free counterions and the solvent quality parameter τ
at increasing polymer concentration opens an interesting
perspective for studying the role played by electrostatic
interactions between solvent and polymer charged groups
in determining the effective overall energetics of poly-
electrolyte-solvent interactions.
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