JOURNAL OF COLLOID AND INTERFACE SCIENCE 206, 424 – 438 (1998)
ARTICLE NO. CS985661
Surfactant Effect on the Stability and Electrorheological
Properties of Polyaniline Particle Suspension
Hyon-Jee Lee, Byung Doo Chin, Seung-Man Yang1 and O Ok Park
Department of Chemical Engineering and Bioprocess Engineering Research Center, Korea Advanced Institute of Science and Technology,
373-1 Kusong-dong, Yusong-gu, Taejon 305-701, Korea
Received January 7, 1998; revised May 8, 1998; accepted May 18, 1998
In this paper, the colloidal stability and electrorheological re-
sponses of semi-conductive polyaniline particles dispersed in a
mineral oil were investigated experimentally. The polyaniline was
synthesized by polymerization of aniline monomer. The surfac-
tants used for the colloidal stability were commercially available
nonionic Span20, Span80, and Span85, which are distinctly dif-
ferent in their molecular structures. Dynamic yield stress of polya-
niline suspension, which possessed the quadratic dependence on
electric field strength at low electric field, exhibited the linear
dependence at high electric field. In addition, the conductivity of
polyaniline particles influenced the electrorheological response
and there existed the optimal conductivity for the maximum yield
stress. In the presence of nonionic surfactants used here, the yield
stress of polyaniline exhibited a local maximum at a certain sur-
factant concentration. The existence of optimal surfactant concen-
tration was confirmed by the surfactant adsorption isotherm. We
hypothesized that below the optimal threshold concentration, the
electrorheological activity was enhanced by the increased interfa-
cial polarization induced by the adsorbed surfactant molecules.
Above the threshold concentration, however, the electrorheologi-
cal activity was degraded by the conduction through the field-
induced surfactant-rich bridge between adjacent particles. This
optimal concentration coincided with the saturation concentration
in the adsorption isotherm. The surfactants used in this study
showed the improved colloidal stability due mainly to the induced
steric hindrance effect. For the colloidal stability, Span80 was the
most effective. However, considering that ER activity comes
mainly from relatively large particles of O(mm), which are mostly
present in our system, Span85 was the best choice for a stabilizing
additive in the present ER suspension. In addition, our results
showed that the presence of the nonionic surfactants considered
here did not cause any sensible degradation at high
temperatures. © 1998 Academic Press
Key Words: electrorheology; semiconductive polyaniline; con-
duction model; nonionic surfactant; yield stress; adsorption
isotherm.
1. INTRODUCTION
In the present study, we consider the effect of surfactants on
the colloidal stability and electrorheological (henceforth ER)
1
To whom correspondence should be addressed. E-mail: smyang@cais.kaist.ac.kr.
0021-9797/98 $25.00
Copyright © 1998 by Academic Press
All rights of reproduction in any form reserved.
responses of a semi-conductive polyaniline particle suspen-
sion. The ER responses are known for a rapid and reversible
change in the suspension viscosity upon inception of an electric
field. These ER responses also accompany changes in the
variety of ER fluid properties, including rheological, electrical,
optical, thermal, volumetric, and acoustic properties. Interest in
this problem stems mainly from its potential applications in
various areas. Among the typical applications of practical
significance are vibration damping (ER dampers and engine
mounts), force transfer such as clutches and valves, and other
hydraulic systems and micro-robotics.
Since the pioneering discovery of ER responses by Winslow
(1), enormous studies have been carried out to understand the
underlying physics of ER responses and thereby to correlate
the ER performance with the material properties of ER fluid.
Generally, ER fluid is a typical suspension composed of mi-
cron-sized polarizable particles dispersed in a nonconducting
medium. The mismatch in conductivities or dielectric proper-
ties between the dispersed particle and the continuous medium
phase induces polarization upon application of an electric field.
The induced particle dipoles, under the action of an electric
field, tend to attract the neighboring particles to one another
and cause the particles to form fibril-like structures, which are
aligned to the direction of the electric field. Because these
fibril-like structures provide additional resistance against fluid
motion, ER fluid behaves like a Bingham fluid in the presence
of an electric field.
To understand the electric-field induced polarization, there
have been a number of postulations and suggestions available
for the mechanisms of ER responses. Typical and plausible
mechanisms include electrostatic polarization (1), overlap of
electric double layers (2, 3), formation of a water bridge (4),
and interfacial polarization (5). The interfacial polarization
mechanism has received some attention due to its versatility for
qualitative and phenomenological explanation of the ER re-
sponses in either recently developed anhydrous systems or
traditional water-containing systems. In reality, however, ER
responses can be hardly explained quantitatively by a single
mechanism and rather depend on variety of physicochemical
variables and operating conditions. A few examples are elec-
424
 STABILITY AND ELECTRORHEOLOGICAL PROPERTIES
trical properties of two contiguous phases, strength and fre-
quency of electric field, pH, temperature, and contents of
dispersed particles and additives.
Similarly, the dynamics in ER response have been studied
and a number of models have been proposed. The simplest one
is the electrostatic polarization model (6), which is based on
the assumption that ER fluid is a suspension of dielectric,
nonconducting particles dispersed in a low dielectric medium.
Consequently, the electrostatic polarization model neglects the
electrokinetic phenomenon associated with free charges and
their transfer. In practice, however, ER fluid possesses inevi-
tably some level of conductivity and free charges, which are
transferred across the electrodes. A number of studies have
modified the electrostatic polarization model to include the
phase conductivity and other parameters (7). Specifically,
among the most important features in the modified models is to
confirm that ER response in the DC field or AC field at low
frequencies is controlled, not by the dielectric mismatch, but
rather by the conductivity mismatch between the particle and
the medium phase (8, 9). For example, the Maxwell–Wagner
model (10) can incorporate the conductivity mismatch into the
ER response at the low frequency field. Thus, the Maxwell–
Wagner model describes the particle polarization accounting
for both the conductivity and dielectric mismatches by employ-
ing the complex dielectric constant as a function of the field
frequency. However, these modified models cannot explain
why the electric field dependence of the yield stress is often
less than quadratic. To explain this nonquadratic dependence
on the field strength, the so-called conduction model was
developed, which considers both the conductivity effect and
the nonlinear conduction between the particles at the high
electric field (11, 12). The conduction model exhibits a qua-
dratic dependence of the yield stress on the electric field
strength at the weak electric field and, at the same time, a linear
dependence at the strong electric field. This is, in general,
typical of the ER materials which possess some level of con-
ductivity.
Despite the numerous investigations discussed above, the
commercially available ER fluid has not been developed yet.
There are many required properties for practical applications of
ER fluids. Of practical importance are high yield stress, low
conductance, the wide range of working temperatures, the low
viscosity in the absence of an electric field, and stability to
maintain the colloidal dispersibility (13). To overcome these
remaining problems, intrinsically polarizable materials and
surfactant additives are often employed in preparation of ER
suspensions. Intrinsically polarizable materials have a number
of advantages over extrinsically polarizable ones in that the
materials can endure a wide range of working temperatures. In
particular, the surfactant plays a key role in promoting the
colloidal stability, as well as in improving the ER effect if
added to a certain threshold concentration. In some cases, the
suspension viscosity can be controlled also by surfactant ad-
dition. Although some reports have been available for the
425
surfactant effect on ER response (14 –18), the control of inter-
facial properties and the stability in ER suspension in the
presence of surfactants have not been fully understood yet.
Nevertheless, systematic assessment for the role of added
surfactant in these electrokinetic phenomena still remains es-
sential for the design of an optimal ER fluid. This is the
primary thrust of the present study.
In the present work, ER suspensions of semi-conductive
polyaniline particles dispersed in a mineral oil were prepared
to examine physicochemical interplay between the material
properties and the ER behaviors modified by the presence of
various types of nonionic surfactants. As we shall see shortly,
the present study provided the practically important results for
the ER activity enhanced by the surfactant addition, as well as
for the optimal electrical and physical properties of the con-
stituent materials. First, we investigated the ER responses in
terms of the mismatches in the electrical properties, which
changed differently for the presence of various types of sur-
factants with different molecular structures. Then, surfactant
effects on the colloidal stability were studied by employing
various techniques such as an UV-light transmittance test and
a sedimentation ratio test. The stability test results were ana-
lyzed in terms of molecular structure of the surfactant in
conjunction with the adsorption isotherm. The results showed
that the optimal surfactant concentration for ER performance
and colloidal stability could be predicted somehow from the
adsorption isotherm. Finally, the surfactant-rich bridge forma-
tion between the adjacent particle surfaces was observed to
examine the current overload at the high surfactant concentra-
tion limit.
2. MATERIALS AND METHODS
2.1. Material Preparation
Dispersed material used in this study was semi-conductive
polyaniline synthesized following the method of MacDiarmid
(19). The aniline solution was prepared by mixing aniline and
chilled hydrochloric acid with continuous stirring. Then, the
polyaniline was synthesized by adding 0.1 M ammonium per-
sulfate solution to chilled aniline solution of the same temper-
ature at 0°C. The initial concentrations of the reactant aniline,
ammonium persulfate and hydrochloric acid were 0.55 M, 0.1
M, and 1 M, respectively. After the reaction was completed,
emerald green polyaniline particles were obtained. These
polyaniline particles were filtered and washed twice with eth-
anol. At this state, the polyaniline possesses conductivity that
is too high to be used as ER material (20). Thus, further
treatment of the polyaniline with 1 N NaOH was required to
reduce the particle conductivity. Particle conductivity can be
controlled also by either a dedoping treatment with another
basic solution or doping treatment. After dedoping with NaOH,
the polyaniline was washed twice once with water and once
with ethanol. After the polyaniline was dried at 80°C in a
426 LEE ET AL.

vacuum oven for 24 h, the samples were ground using mortar

and pestle and dried again in a vacuum oven. Prepared polya-
niline particles exhibited a broad size distribution with mean
diameter of 32 mm. To avoid other impurities in the particle
phase, the polyaniline particles were sieved with a No. 100
mesh of 150 mm. Finally, prepared polyaniline particles were
stored in a desiccator.
To examine the effect of particle conductivity on the ER
response, the polyaniline particles with various conductivities
were prepared by changing the dedoping time; namely, 30 min,
1 h, 5 h, 10 h, etc. Electric properties of the polyaniline
particles such as the dielectric constant or conductivity were
changed with the dedoping time.
FT-IR spectroscopy was used to identify the chemical struc-
ture of the prepared polyaniline. The infrared spectrum of the
polyaniline samples utilized in this study was compared with
that reported in the literature. Although the detected IR spectra
were not reproduced in this paper, the present sample had
peaks at the same wave numbers and agreed with those of Ref.
(21). The size distribution of the polyaniline particles was also
determined by a centrifugal particle size analyzer (Shimadzu,
SA-CP3). As expected, the particle diameter of the sieved
sample was smaller than 150 mm and showed also a relatively
broad spectrum between O(nm) and 150 mm. However, the ER
particle used here are mostly O(mm) in size and the number
density of O(nm) particles is very small. Thus, the fibrillated
structure which creates the yield stress comes mainly from the
mostly present large O(mm) particles. Moreover, for very small
particles of O(nm), the random Brownian contribution tends to
dominate the electrostatic contribution which is responsible for
the ER effect.
In addition, the particle microstructure was observed by
TEM (transmission electron microscopy), and the result is FIG. 1. TEM image of polyaniline particles: (a) magnification 312; (b)
shown in Fig. 1. It can be noted that the particles are composed magnification 10000.
of many primary particles. Although the particle shape is
irregular, the particles can be assumed, in effect, to be spher-
ical. In addition, the particle surface area was measured by study is to investigate the effect of surfactant on both the
BET, and the corresponding result is contained in Table 1. It colloidal stability and the ER responses in terms of its concen-
can be deduced from Table 1 that the particle surface area is tration and molecular structure. To do this, we chose three
relatively large and most of the particle pores are macro-pores different nonionic surfactants, namely Span20, Span80, and
of 21.7 nm in diameter. Span85. The surfactants are structurally similar but different,
To examine the rheological and dielectrical properties, both in the length of the hydrophobic chain and in the number
polyaniline suspensions were prepared by simply adding the of hydrophilic polar groups. It is noteworthy that the number
desired amount of polyaniline particles in the mineral oil next to Span represents the relative intensity of hydrophobicity.
(Sigma), which was used as a continuous phase in the present To examine the surfactant effect, addition of the desired
study. The mineral oil itself behaves like a Newtonian fluid and amount of surfactant to the mineral oil was followed by the
its physical properties such as viscosity, density, and relative addition of the polyaniline particle to the surfactant solution
dielectric constant are contained in Table 1. Also included in until the content of the particle phase reaches 10 wt% on the
Table 1 are the various physical properties of the polyaniline total suspension weight base. Properties of the surfactants used
particles prepared here. In the present study, 10 wt% polyani- in this study are summarized in Table 2.
line suspension was used, and at least 18 g of the suspension
2.2 Rheological Measurements under Electric Field
sample was required for both rheological and dielectric mea-
surements. Rheological behavior of the polyaniline suspension was
As mentioned previously, the main objective of the present measured by PHYSICA rheometer (PHYSICA, MC120).
 STABILITY AND ELECTRORHEOLOGICAL PROPERTIES
TABLE 1
Properties of Materials Used in This Study
(a) Properties of polyaniline and mineral oil
Physical properties of particle phase
Density
Shape
Size
Relative dielectric constant
BET surface area
Macro pore volume (1 , diameter , 300 nm)
Micropore volume
Average pore diameter
Physical properties of continuous phase (light white oil)
Density
Viscosity
Relative dielectric constant
(b) molecular structure of polyaniline
Steady shear stress versus shear rate of the ER suspension
under a steady electric field was measured using a Couette cell
(PHYSICA, Z3 DIN). The PHYSICA rheometer was modified
for application of the large electric fields with a special mea-
suring device (PHYSICA, TEZ 150E). Diameters of the cup
and bob in the Couette cell were 27 mm and 25 mm, respec-
tively, with a 1-mm gap size.
The electric field for rheological measurement was applied
by a high voltage power supply (PHYSICA, HVG5000) to the
cylinder cup with the bob grounded. The intensity of voltage
could be easily controlled in the range of 0 – 4 kV. Temperature
of the cell was controlled using an outer water-circulating
jacket. Most of the experimental data were obtained in the DC
field. If the AC field was used, its frequency should be speci-
fied. Otherwise, the DC electric field was generated.
2.3 Dielectric Measurements
Dielectric properties of the polyaniline particles and the
polyaniline suspension were measured by a dielectric analyzer
(TA Instruments, DEA 2970). Dielectric properties of the
polyaniline particles were measured using a parallel-plate ce-
ramic sensor in the temperature range of 25°C–95°C and in the
frequency range of 101Hz–105Hz, as noted in Fig. 2. Dielectric
properties of the polyaniline suspension were measured using
a remote single surface sensor at room temperature.
427
2.4 Microscopic Observation
The microstructure evolution of the polyaniline suspension
under the action of an electric field was observed by a video
camera (Vicon, VC285) attached to an optical microscope
Polyaniline (American Optical, Microstar). The video image was processed
(1 h dedoped)
by a personal microcomputer. A schematic of the apparatus
1.20 g/cm3 and detailed configuration of the electrodes are illustrated in
irregular Fig. 3A. The gap between the copper electrodes was main-
32 mm tained at 1 mm and a high voltage power supply (Glassman)
4.8 (at 1 Hz) was employed to provide the electric field. As an example, Fig.
57.3248 m2/g
3B shows changes in the microstructure in a dilute polyaniline
0.306551 cc/g
0.000528 cc/g suspension under various electric field strengths. Upon appli-
21.69748 nm cation of an electric field, the fibril-like particle structure could
be observed. And chain strings got thicker as the electric field
Mineral oil strength increased.
As we shall see shortly in Section 3.7, for a given electric
0.84 g/cm3 field there exists a critical surfactant concentration above
0.024 Pa s which the surfactant-rich bridge at the interstice between the
2.1 adjacent particles was formed under the electric field. How-
ever, it is very difficult to observe the surfactant-rich bridge
formation between the small and irregular polyaniline parti-
cles. Instead, the mono-dispersed large glass beads of 100 mm
in diameter were used to examine the surfactant-rich bridge
formation with various surfactant concentrations under the DC
field.
2.5. Adsorption Isotherm
The adsorption isotherm of the surfactant molecules was
obtained by measuring its concentration in the continuous
mineral oil phase before and after contact with the polyaniline
particles. To do this, the surfactant-in-oil solution at various
surfactant concentrations was mixed with the polyaniline par-
ticles in a test tube, which was then placed in a shaking
incubator for 24 h at a constant temperature of 25°C. The
solution was then centrifuged at 12,500 rpm for 30 min (Vision
Scientific, VS-1500). Clear supernatant at the top was decanted
to measure the surfactant concentration. The surfactant con-
centration in the supernatant was determined by an UV-Vis
spectrophotometer (Varian, Cary1/3) at a wavelength of 270
nm. Then, the adsorbed concentration was calculated by sub-
tracting the surfactant concentration in the supernatant from the
initial surfactant concentration.
2.6. Stability Test
Stability of the polyaniline suspensions was examined by
various methods such as an UV transmittance test and a sedi-
mentation ratio test. In the UV transmittance test, changes in
the transmitted UV light passed through a given point of the
prepared sample were measured as a function of time. An
increase in the transmittance with time at a given point implies
that sedimentation or flocculation of the colloidal system is
occurring. Through these results, the relative colloidal stability
of the suspension can be estimated, at least qualitatively.
428 LEE ET AL.

TABLE 2
(a) Properties of surfactants

Commercial Solubility in
name Chemical composition «9 HLB M.W. water/mineral oil

Span 20 Sorbitan monolaurate 5.57 8.6 346 Insoluble/soluble

Span 80 Sorbitan monooleate 4.16 4.2 428 Insoluble/soluble
Span 85 Sorbitan trioleate 3.37 1.8 956 Insoluble/soluble

(b) Molecular structures of the surfactants; Span20, Span80, and Span85.

The sedimentation ratio test is a simple naked-eye observa-
tion of sedimentation or flocculation. A set of the samples were
placed in capped test tubes and observed for 100 h. During this
test time interval, the height of the phase separation between
the particle-rich phase and the relatively clear oil-rich phase
was measured as a function of time. Then, the sedimentation
ratio, defined by the height percentage of the particle-rich
phase, relative to the total suspension height, can be readily
evaluated.

3. RESULTS AND DISCUSSION

3.1. Effects of Dedoping Time on the ER Properties

FIG. 2. Dielectric constant of polyaniline dedoped for 1 h as a function of
temperature and the AC field frequency.
In this subsection, we will consider the effect of polyaniline
particle conductivity on ER properties. Since the major feature
of ER fluids is the yield stress, the dynamic yield stress is
generally used as a representative ER property. To illustrate the
general response of ER fluid, steady shear stress versus shear
rate is shown in Fig. 4A for 10 wt% polyaniline suspension in
mineral oil under various electric field strengths. In this plot,
the polyaniline particle dedoped for 1 h was used. The polya-
niline suspensions behave like Newtonian fluid in the absence
of the electric field. As noted from Fig. 4A, however, the
presence of the electric field induces both the dynamic yield
stress and the significant deviation from Newtonian behavior at
low shear rates (22).
In Fig. 4B, the dynamic yield stress ty is plotted as a
function of the electric field strength (E) in a logarithmic scale.
One thing worthwhile noticing is that the nonlinear quadratic
dependence of the dynamic yield stress on the electric field
strength at the weak electric field switches to a nearly linear
 STABILITY AND ELECTRORHEOLOGICAL PROPERTIES 429

is very difficult to measure accurately the conductivity of

the polyaniline particle, which is much lower than 1026
S/cm. However, it can be seen indirectly from Fig. 5A that
the particle conductivity decreases monotonically as the
dedoping proceeds. It is noteworthy at this point that, espe-
cially under a DC field, a conductivity mismatch between
the two contiguous phases and the corresponding interfacial
polarization strongly influence the ER behavior. As a result,
the optimal conductivity mismatch between the two phases
is the most important factor in the ER effect driven by a DC
field. It is thus essential for the successful design of an ER
material to understand the effects of structural and compo-
sitional factors that influence the conductivity mismatch of
the ER suspension. The results showed that the optimal
dedoping time was 1 h for the prepared polyaniline, as
shown clearly in Fig. 5B. The optimal conductivity mis-
match, which gives the maximum ER effect, would be
simply the largest that could be achieved. In practice, how-
ever, the upper limit of particle conductivity is imposed by
the electric current overload, which inevitably deteriorates
the ER performance. This is why we dedoped the polyani-
line particle to avoid the current overload. In the subsequent
studies, we used the polyaniline particle dedoped for 1 h,
which ensured the most effective ER responses.
FIG. 3. (a) Schematic of microscopic observation system and (b) micro-
structure formation under different AC field strengths.

dependence at the strong field. This nonuniform dependence on

the field strength is typical behavior observed in the ER fluid of
conductive particles and can be explained in terms of the
conduction model (11, 12). For a DC or low frequency AC
field the particle interactions will be controlled, not by the
permittivity mismatch, but rather by the conductivity mis-
match. In a low DC field limit, conduction-induced surface
charges would be linear in the electric field strength, resulting
in a quadratic dependence on the field. Meanwhile, the less
steep dependence in high DC fields arises from a nonlinear
relationship between the current and field strength in the min-
eral oil. Thus, the nearly linear dependence at the high field, as
observed in the present work, would require a nonlinear con-
duction mechanism which induces a surface charge propor-
tional to the square root of the field strength.
Now, let us consider the conductivity effect on the ER
responses. As mentioned previously, polyaniline particles
with different conductivities were prepared by varying the
dedoping time. We used a 1 N NaOH solution as a dedoping
agent and changed the dedoping time to control the particle
conductivity. As the dedoping time increased, the particle
conductivity was reduced. This is evident from Fig. 5A in
which the current density through the ER fluid is plotted
versus the dedoping time. Also shown in Fig. 5B are FIG. 4. (a) Steady shear stress versus shear rate for 10 wt% polyaniline
changes in the dynamic yield stress as a function of the suspension under various electric field strengths (E 5 0.0, 1.0, 2.0, 3.0, 3.5, 4.0
dedoping time for various electric field strengths. In fact, it kV/mm from the bottom). (b) Yield stress as a function of the field strength.
430 LEE ET AL.

FIG. 6. Yield stress as a function of Span20 concentration for 10 wt%

polyaniline suspension for various field strengths.

structure. The detailed discussion on this matter will follow

FIG. 5. (a) Current density and (b) dynamic yield stress as a function of
the dedoping time of polyaniline. The suspension contains 10 wt% of polya-
niline particles with no surfactant present.
shortly.
Beyond the optimal surfactant concentration for a maximum
yield stress, the dependence on the electric field strength be-
came weak, as shown in Figs. 6 and 7. In some cases, mea-
surement of the dynamic yield stress did not provide reliable
data at high surfactant concentration, due to the electric current

3.2. Surfactant Effects on the Rheological Properties

of ER Suspension

Let us then consider the surfactant effects in the ER re-

sponses. Actually, the main objective of surfactant addition is
to promote the colloidal stability. As we shall see shortly,
however, the presence of small amount of the surfactant mol-
ecules can also enhance the ER effect (16, 17). In Fig. 6, the
dynamic yield stress is plotted versus the concentration of
surfactant Span20 for various electric field strengths. Also
included in Fig. 7 is the corresponding result for Span85 for the
same set of parameters as in Figure 6. Since the behaviors of
dynamic yield stress in the presence of Span80 were very
similar to the results for Span20, the corresponding plot was
not reproduced here. As noted from Figs. 6 and 7, the dynamic
yield stress was initially increased, passed through the maxi-
mum, and then exhibited a monotonic decrease which is inde-
pendent of the type of surfactant. The surfactant concentration,
which gives rise to a maximum yield stress, is not sensitive to
the applied electric field strength (E) but does depend on the
type of surfactant. Dependence of the optimal threshold con-
centration on the type of surfactant can be explained through FIG. 7. Yield stress as a function of Span85 concentration for 10 wt%
the adsorption behavior, in conjunction with its molecular polyaniline suspension for various field strengths.
 STABILITY AND ELECTRORHEOLOGICAL PROPERTIES 431

optimal threshold value, independently of the electric field

strength. As shown in Fig. 9, similar trends were also observed
for Span85, although the optimal threshold concentrations, at
which the current density experiences rapid increase, are dif-
ferent from one another. The abrupt increase in the current
density arises from the current passage through the surfactant-
rich bridge formed at the interstice between the neighboring
particles. Of course, the excess surfactant molecules in the
medium phase that cannot participate in adsorption increase the
conductivity of the continuous phase. However, changes in the
conductivity are not expected to be appreciable for such small
amounts of the surfactants. Thus, the abrupt increase in the
current density is due mainly to the surfactant-rich micro-
domain formed at the interstice between the nearby particle
surfaces.

3.3. Surfactant Effects on the Dielectric Properties

of ER Suspension
Until now, we investigated several material parameters
that ensure the optimal ER effect. First, the particle conduc-
FIG. 8. Current density versus the field strength for 10 wt% polyaniline
suspension at various Span20 concentrations. tivity effect was investigated to verify the existence of an
optimal conductivity mismatch, which gives a maximum
yield stress. Second, the optimal surfactant concentration
overload for our apparatus induced by increase in the suspen- was also determined for a maximum yield stress. However,
sion conductivity. The current overload, which also degrades the previous experiments focused only on the ER effect in a
the ER performance, should be prohibited for practical appli- DC field. To examine the ER responses in an AC field,
cation of ER fluids. Possible explanations, for these behaviors dielectric properties are certainly required since the dielec-
beyond the optimal threshold concentration, arise from either tric mismatch is a decisive factor in generating the ER
the conduction through the medium phase or the overloaded phenomena in an AC field.
current passage through the surfactant bridge between the In this subsection, we consider, thus, the dielectric behaviors
nearby particles. At this point, it should be noted that the
surfactant used here has larger conductivity than the polyani-
line particles and the continuous mineral oil is relatively non-
conductive. Consequently, conduction through the medium
phase is caused by increase in the medium conductivity owing
to addition of the excess amount of surfactant. Further, both the
surfactant molecules adsorbed on the particle surface and those
in the bulk phase are transported toward the interstice between
the nearby particles under the action of the electric field. As we
shall see shortly in Section 3.7, the generation of a locally high
field at the interstice, which is responsible for the surfactant
transport toward the gap, is again due to the conductivity
mismatch as noted above. The enriched surfactant phase at the
interstice acts as a bridge through which the electric current
passes (16, 17).
Figures 8 and 9 can provide possible evidence for these ER
responses in the presence of the surfactants. In these Figs. 8
and 9, the current densities are plotted as a function of the
electric field strength for various concentrations of surfactants
Span20 and Span85, respectively. In this case, the current
density observed in the presence of Span80 was similar to that
for Span85 and, thus, the corresponding figure was not needed.
It can be readily seen from Fig. 8 that the current density FIG. 9. Current density versus the field strength for 10 wt% polyaniline
increases abruptly as the Span20 concentration exceeds the suspension at various Span85 concentrations.
432 LEE ET AL.

3.4. Surfactant Adsorption Behavior at Polyaniline Surface

To correlate the ER effect and the physical properties of the
added surfactants in the ER suspension, we begin by consid-
ering differences in the surfactant molecular structures. Mo-
lecular structures of the surfactants used in this study are
contained in Table 2. In general, the longer the hydrophobic
tail, the weaker the hydrophilicity. Moreover, both the conduc-
tivity and dielectric constant become smaller for the surfactant
with the longer hydrophobic tail (23). Thus, the limiting sur-
factant concentration, which can avoid the electric current
overload, becomes higher for the longer hydrophobic tail. This
is obviously seen from comparison of Figs. 6 and 7, in which
the data points at the highest surfactant concentrations corre-
spond to the limit point imposed by the current overload.
Specifically, the limiting surfactant concentrations, above
which the electric field overload occurred, were 2.5 wt%, 3.0
wt%, and above 5.0 wt% for Span20, Span80, and Span85,
respectively. However, the optimal surfactant concentration for
a maximum yield stress cannot be explained readily in terms of
FIG. 10. Dielectric constants as a function of the AC field frequency the surfactant molecular structure. It is, thus, necessary to
polyaniline, mineral oil, and 10 wt% polyaniline suspension. examine the interfacial phenomena and the surfactant-induced
interfacial polarization. To do this, the surfactant adsorption on
the polyaniline particle was studied here. In addition, the
in the presence or absence of the surfactant. It is observed that adsorption behavior can also provide important information in
the ER activity of the polyaniline suspension without any the colloidal stability.
surfactant decreased rapidly, especially as the frequency of the As clearly seen from Fig. 12, the adsorbed amounts of
electric field increases. Eventually, the ER effect almost van- surfactants, Span20 and Span80, were almost the same for a
ishes at the field frequency above 50 Hz. As shown in Fig. 10, given concentration of the medium at equilibrium. On the other
the dielectric mismatch between the particle and the medium hand, the adsorbed amount of Span85 is very small, compared
becomes small with the increase in the electric field frequency. with those for the other two types, Span20 and Span80. The
The reduced dielectric mismatch is responsible for the vanish-
ingly weak ER effect at the high frequency limit.
In the presence of the surfactant, dielectric behaviors of
the particle and the medium became different from those
observed for the suspension without any surfactant. Conse-
quently, dielectric mismatches between the particle and the
medium are expected to change with the added surfactant. It
is thus tempting to expect that the added surfactant may
activate the ER suspension, even in the alternating electric
field. However, no sensible effect was induced by the sur-
factant addition. In Fig. 11 the dielectric constant of the
polyaniline suspension in the presence of Span85 is plotted
as a function of the field frequency for various concentra-
tions of Span85. Similar trends were also observed for
Span20 and Span80. As noted, the dielectric constant of the
suspension was increased with the surfactant concentration,
since the added surfactant certainly increased the dielectric
constants of both the constituent phases. However, the in-
creases in both the phases counterbalance each other and the
mismatch between them was not enhanced appreciably. As
a result, the ER effect in the alternating electric field was not
changed appreciably by the presence of the nonionic sur- FIG. 11. Dielectric spectra of 10 wt% polyaniline suspension as a function
factants. of the AC field frequency for various Span85 concentrations.
 STABILITY AND ELECTRORHEOLOGICAL PROPERTIES
FIG. 12. Surfactant adsorption isotherm on the polyaniline particles in
mineral oil. Equilibrium concentration is the surfactant concentration in the
continuous Phase.
difference in the adsorption amounts is associated with the
molecular structures. In fact, the hydroxyl group is contained in
the head part of the surfactant anchors on the polyaniline
surface. The driving force in this adsorption process originates
from the weak hydrogen bond between the 2NH functional
group in the polyaniline phase and the 2OH functional group
in the surfactant head. And the surfactant tail part, which tends
to align toward the medium, is the long hydrophobic hydro-
carbon chain.
In particular, Span20 and Span80 have the same type of head
parts with two 2OH groups. These head parts, which are
bulky, compared with the tail parts, play a major role in
determining the adsorption characteristics. Thus, the similarity
in the head parts of Span20 and Span80 explains the almost
same adsorption behaviors as indicated by Fig. 12. Meanwhile,
the head part of Span85, which possesses only one hydroxyl
group, exhibits relatively weak adsorption affinity to the par-
ticle surface, compared with those of Span20 and 80. In addi-
tion, the tail part of Span 85, which is much longer and bulkier
than those of Span20 and Span80, tends to induce considerable
interference to the adsorption of the other nearby molecules.
As a consequence, the coverage of Span85 molecules over the
polyaniline particle is low, compared with the cases of Span20
and Span80.
The present adsorption behaviors in terms of molecular
structure are also consistent with the results discussed concern-
ing the surfactant effect on the dynamic yield stress. As noted
from Figs. 6 and 7, the optimal concentrations of Span20 (and
Span80) are the same and about 1 wt% while that of Span85 is
about 2.5 wt%. In fact, these optimal concentrations corre-
433
spond exactly to the saturation values in the adsorption iso-
therms, as clearly seen in Fig. 12. Above these concentrations,
the surfactant molecules are more likely to reside in the me-
dium phase rather than to adsorb to the particle surface in the
absence of an electric field. In the presence of the electric field,
however, the enriched surfactant molecules in the medium
phase will gather into the interstice between the nearby particle
surfaces in which a nonuniformly high electric field is gener-
ated. As previously indicated, the surfactant-rich bridge be-
tween the adjacent particles is relevant to degradation of the
ER properties at the high surfactant concentration limit.
3.5. Surfactant Effects on the Stability of ER Suspension
Until now, we focused on the surfactant effect on the ER
responses. In the present study, the main objective of the
surfactant addition is to enhance its colloidal stability and
thereby improve the ER properties for practical applications.
Surfactants that are compatible with the present ER suspension
are limited. The surfactants to be used should possess both the
proper solubility into the oil (i.e., medium) phase and the
appropriate conductivity. The surfactant conductivity must be
low to prevent current overload of the electric device. If the
surfactant has a relatively much higher conductivity than the
particle, most of the current will pass through either the sur-
factant-dissolved medium or the electric-field induced bridge
of the surfactant-rich phase, even at low surfactant concentra-
tion. In this case, the ER activity decreases or eventually
vanishes. In some cases, the ER device will be damaged by the
current overload.
To overcome these limitations, we thus chose the nonionic
surfactants. The nonionic surfactant used in this study will
induce mainly the steric hindrance effects for the stability
between the suspending particles. We used various methods to
investigate the ER suspension stability. In general, ER suspen-
sions are a highly concentrated system and difficulties arise in
examining the ER suspension stability accurately. In the
present study, we examined indirectly the effect on the colloi-
dal stability by observing the sedimentation behaviors in the
presence of three different surfactants at various concentra-
tions. The first observation method is the transmittance test, in
which we used the polyaniline particles smaller than 50 mm in
diameter and diluted to 1 wt% particle concentration. This low
particle concentration is required for an appropriate UV light
transmittance. To maintain the surfactant content at the same
level as in the original concentrated suspension, the sample
was prepared first by extracting a small amount from the
original 10 wt% suspension and then diluting it with the
medium oil that has the same surfactant content as in the
equilibrated original suspension.
Figures 13A–13C show the transmittance change as a func-
tion of time in the presence of Span20, Span80, and Span85,
respectively. In these experiments, the transmittance was mea-
sured at about 3 cm above the bottom and the overall sample
434
FIG. 13. Transmittance changes as a function of the settling time for 1 wt% polyaniline suspensions in the presence of (a) Span20, (b) Span80, and (c)
Span85, each at various concentrations.
height was 4.5 cm. It can be easily seen that the transmittance
is initially zero everywhere, since most of light passed through
the sample is absorbed and scattered by the well-dispersed
polyaniline particles. As the settling proceeds, however, the
transmittance increases slowly at the initial stage and experi-
ences rather rapid elevation when most of the polyaniline
particles settle down below the measuring point. These general
features are preserved, independently of the types of surfac-
tants and their concentrations, as illustrated in Figs. 13A–13C.
However, the sedimentation is retarded by the presence of the
LEE ET AL.
surfactants which prevent particle aggregation. Consequently,
the sedimentation rate is reduced as the surfactant concentra-
tion increases.
Another major feature inherent in the transmittance test for
the colloidal dispersion stability at zero electric field is that
Span80 gives the most significant stabilizing effect among the
surfactants considered here. When the surfactant molecules are
present in the polyaniline particle suspensions, the surfactant
molecules adsorbed on the particle surface mainly affect its
colloidal stability. Thus, possible explanations can be given in
 STABILITY AND ELECTRORHEOLOGICAL PROPERTIES
FIG. 14. Sedimentation ratio as a function of the settling time for 10 wt% polyaniline in mineral oil suspension in the presence of (a) Span80 and (b) Span85,
each at various concentrations.
terms of both the surfactant molecular structures and their
surfactant adsorption behaviors. As we mentioned in the pre-
vious subsection, the adsorbed amounts of Span20 and Span80
molecules are almost the same and much larger than those of
Span85. Therefore, the number of Span85 molecules that in-
volve stabilizing the suspension is very small, compared with
the case in which either Span20 or Span80 is dispersed. On the
other hand, the tail part of the surfactant also plays a central
role in the steric hindrance between the particles and usually
the stability of suspension is enhanced by the longer tail part.
In view of the long tail part of Span80, compared with Span20,
Span80 is more effective than Span20. Combining the individ-
ual effects associated with both the number of adsorbed mol-
ecules and the length of the tail part is clearly indicative of the
fact that Span80 plays the most effective role in stabilizing the
polyaniline suspension.
However, the transmittance test alone does not provide
sufficient information on the stabilization effect of the surfac-
tants. Although the transmittance test shows that Span80 is the
most effective stabilizer, a simple naked-eye observation of the
sedimentation gives quite different results. In general, when
sedimentation proceeds in a suspension, the suspension is
divided into three unique zones, namely, a highly packed
sediment zone, a concentrated suspension zone, and a super-
natant zone of clarified liquid containing very tiny particles. As
the sedimentation time passes, the heights of the sediment and
clarified liquid zones grow. In the presence of Span80, the
macroscopic phase boundary between the concentrated suspen-
sion and clarified liquid zones moves down, leaving very tiny
particles behind. In the cases of Span20 and Span85, however,
the supernatant zones do not contain that many tiny particles
435
and are very clear, compared with the case of Span80. In the
supernatant zone in the presence of Span 80, the suspended
particles were very small and the mean diameter was only 0.3
mm. Thus, Span80 is very effective in stabilizing tiny small
colloidal particles, compared to Span20 and Span85. Indeed,
Span80 was also shown to be the most effective stabilizer by
the transmittance test, since the relatively high density of tiny
particles in the supernatant zone can also absorb and scatter the
light. Meanwhile, as we mentioned earlier, the ER effects come
mainly from the relatively large particles of O(mm) which are
mostly present in our suspension system. Consequently,
Span80 may not be the best choice for the effective stabilizer
in ER fluid.
To choose the best surfactant stabilizing “true” ER suspen-
sion, the stability of the ER suspension was examined through
the sedimentation ratio test. Although the sedimentation ratio
test cannot give thorough information on the suspension sta-
bility, it is widely used because of its simplicity and conve-
nience. In addition, it has no limitation to the particle and
medium properties and their concentration ranges. In the
present sedimentation ratio test, we observed the settling of the
macroscopic phase boundary between the concentrated suspen-
sion and the clarified “supernatant” liquid. Thus, the sedimen-
tation ratio test reflects the role of the surfactant in stabilizing
the “ER effective” suspension phase and does not take into
account the stability of very tiny colloidal particles. In Figs.
14A and B, the sedimentation ratio is plotted as a function of
the settling time at various concentrations of Span80 and
Span85, respectively. These figures show that Span85 is the
most effective in stabilizing relatively larger “ER effective”
particles, although not effective for tiny small particles. Also
436 LEE ET AL.
shown from the present sedimentation ratio test was that Span
20 was slightly behind Span80 in stabilizing the ER suspen-
sion. The pronounced stabilizing effect of Span85, especially
for a concentrated suspension can be explained as follows:
First, the settling velocity is increased by the particle floccu-
lation at a highly concentrated system, in which the gravita-
tional force is dominant. In these circumstances, the sedimen-
tation ratio is relevant only to the particle packing density.
Second, the bulkiness of adsorbed surfactant molecules be-
comes a decisive factor in the concentrated suspension. In
many cases, the adsorbed surfactant molecules either enhance
the stability by steric hindrance or destabilize the suspension
by agglomerating the adjacent particles covered with the sur-
factant molecules. However, destabilizing via flocculation can-
not be expected for the nonionic surfactants considered here,
which have very short hydrocarbon chains, compared with
polymeric surfactants. Indeed, Span85, with the longest tail
part among the surfactants used here, induces the most effec-
tive hindrance for large particles and thereby stabilizes most
effectively the ER effective particle phase.
In summary, Span80 can provide the best suspension stabil-
ity when very tiny particles in the clarified supernatant zone are
taken into account. Meanwhile, Span85 prevents most effec-
tively the aggregation of relatively large particles in the polya-
niline suspension. Actually, to get the satisfactory ER activity
and suspension stability, Span85 exhibited the best perfor-
mance in the polyaniline/mineral oil suspension. The addition
of Span85 up to 2.5 wt% gives rise to the increase in both the
stability and the yield stress and their enhancements are satis-
factory, compared to the cases of Span20 and Span80.
3.6. Temperature Effects
In the practical application of ER fluids, the sustained ER
activity over wide range of temperature is certainly needed. In
the case of water-activated ER suspension, temperature eleva-
tion causes the evaporation of adsorbed water, and conse-
quently the ER effect decreases as the suspension temperature
increases. However, our polyaniline suspension sustains good
ER activity even at high temperatures, as seen in Fig. 15. This
is because the ER activity of our suspension arises mainly from
the bulk property of polyaniline particle (22). For the present
system of the polyaniline particle dispersed in mineral oil, the
upper limit for the temperature is imposed by the current
overload due to the conductivity enhancement with the rise in
temperature. In fact, the experimental data represented in Fig.
15 were taken until the temperature reached a value at which
the current overload occurred.
In the presence of the surfactant, the temperature effect on
ER activity became more complicated. As the temperature
varies, not only the electrical properties of the particle and the
medium phases, but also the adsorption and desorption behav-
iors of the surfactant change. As mentioned previously, the
conductivities of the particle and medium phases change with
FIG. 15. Temperature dependence of the dynamic yield stress for 10 wt%
polyaniline suspension for various field strengths.
the variation in temperature, which in turn modifies the sur-
factant adsorption and desorption at the particle interstice un-
der the application of the electric field. This is because the
electric field creates the surfactant-rich phase at the interstice
of the high-field region, which is established by the conduc-
tivity mismatch between the particle and the medium phase.
Due to these complicated phenomena, the ER fluid containing
the nonionic surfactant also showed nearly constant ER activity
as shown in Fig. 16. But the detailed mechanism should be
studied further. In this figure, it can be easily expected that the
presence of the surfactant enhances the temperature effect in
increasing the current density (or equivalently the conductiv-
ity) and, consequently, the onset temperature for the current
overload is low, compared to that of the surfactant-free system.
In Fig. 17, the temperature effects on the colloidal stability
are illustrated by plotting the sedimentation ratio versus time
for 10 wt% polyaniline in the mineral oil suspension. Here, the
content of surfactant Span85 is fixed at 2.5 wt% and the
temperature ranges from 5°C to 85°C. As expected, the sedi-
mentation rate is increased and colloidal stability deteriorates
as the temperature is elevated. This is not only because the
viscosity decreases but the surfactant desorption proceeds at
high temperatures. Although the corresponding plot is not
reproduced, the sedimentation test was performed in the ab-
sence of the surfactant at various temperatures. The results
showed that the surfactant effect in improving the colloidal
stability persisted in the range of the temperature, but the
degree of improvement became smaller as the temperature
rose. Thus, it can be certainly deduced that the deteriorated
stability at high temperatures is due partly to the surfactant
desorption.
 STABILITY AND ELECTRORHEOLOGICAL PROPERTIES 437

the bridge of the surfactant-rich phase is formed at the

interstice between the surface of adjacent glass beads. This
surfactant-rich bridge between the particles causes the cur-
rent overload, which degrades inevitably the ER activity at
high surfactant concentration, as confirmed earlier.

4. CONCLUSIONS

In the present study, an ER suspension was prepared by

dispersing semi-conductive polyaniline particles in a min-
eral oil to investigate the added surfactant effects on ER
responses and its colloidal stability. The conclusions are as
follows:
The dynamic yield stress that exhibited a nonlinear quadratic
dependence on the field strength at the weak electric field
showed a linear dependence at the strong electric field, which
is consistent with the conduction model. Dedoping treatment
with 1 N NaOH solution for 1 h was shown to be the most
effective in controlling the particle conductivity to generate an
optimal conductivity mismatch.
FIG. 16. Temperature dependence of the dynamic yield stress for 10 wt%
polyaniline suspension in the presence of 1.5 wt% of Span80 for various field The threshold surfactant concentration, above which the
strengths. dynamic yield stress was reduced, was dependent upon the
types of surfactant. The threshold concentrations for Span20,
Span 80, and Span85 considered here were identical to those at
3.7. Microstructure Observation which the adsorption was saturated at equilibrium. At the
surfactant concentration far above the threshold value, the
Finally, let us consider the electric field induced microstruc-
onset of current overload deteriorated the ER activity. The
ture in ER suspension. When the DC field is applied, migration
abrupt increase in the current density was due mainly to the
of the polyaniline particle arises either from electrophoresis
surfactant-rich micro-domain formed at the interstice between
(which is induced by the net particle charge) or dielectrophore-
sis (induced by nonhomogeneity of the electric field). Under
these circumstances, the particles become more likely to con-
tact the neighboring particles. Due to the fluid motion induced
by the electric field, the polyaniline particles were moving
around rapidly and colliding with each other. Finally, fibril-like
structures of the polyaniline particles were produced with
alignment to the direction of the electric field.
As we mentioned earlier, the surfactant-rich bridge be-
tween adjacent particles evolves above some critical surfac-
tant concentration at a given electric field strength (16). To
confirm the surfactant-rich bridge formation, an experimen-
tal simulation on the surface of glass beads was carried out.
Because of the difficulty in observing the surfactant struc-
ture formation between the irregular shaped small polyani-
line particles, we used instead mono-dispersed glass beads
of 100 mm in diameter. It can be easily expected that a low
concentration limit, the bridge structure of the surfactant-
rich phase can hardly be established between the glass
beads. Indeed, the microphotograph in Fig. 18A taken from
the suspension containing 0.5 wt% of Span20 shows any
evidence for the surfactant-rich bridge formation at this low
surfactant concentration. However, as shown in Fig. 18B, FIG. 17. Sedimentation ratio as a function of the settling time for 10 wt%
the externally applied electric field induces the surfactant- polyaniline in mineral oil suspension with 2.5 wt% of Span85 at various
rich bridge evolution at high surfactant concentration and temperatures.
438 LEE ET AL.
FIG. 18. Surfactant-rich phase formed at the interstice between the glass beads (100 mm in diameter) in the presence of (a) 0.5 wt% of Span20 and (b) 1.5
wt% of Span20 under the electric field in the horizontal direction.
the particle surfaces. The bridge structure evolution in the
surfactant-rich phase between the adjacent particle surfaces
was confirmed by a microscopic observation. This work has been supported by a grant from KAIST-SK Corp. Coopera-
tive Research Program.
Dielectric mismatch between the particle and the medium
phase was vanishingly small at the high frequency limit in an
AC field. The reduced dielectric mismatch led to a very weak
ER effect at the high frequency AC field. The presence of the
1.
nonionic surfactants considered here increased the dielectric 2.
properties both of the contiguous phases and was not effective 3.
in improving the dielectric mismatch. As a consequence, the 4.
nonionic surfactants could not produce any appreciable en- 5.
6.
hancement in the ER activity in an AC field.
7.
An UV-light transmittance test and a sedimentation ratio test 8.
for the colloidal stability showed that Span80 produced the 9.
most significant stabilizing effect if very tiny colloidal particles 10.
were taken into account. Meanwhile, considering that the ma- 11.
12.
jor contribution to the ER activity comes from relatively large
13.
particles in our system, Span85 was shown to be the most 14.
effective surfactant for the colloidal stability, although not so 15.
effective for tiny small particles as Span80. This is due to the
fact that Span85 with the longest and bulkiest tail part among 16.
17.
the surfactants used here induces the most effective steric
18.
hindrance to aggregation of large particles.
The present polyaniline suspension sustained good ER ac- 19.
tivity even at high temperature, and the allowable temperature
was bound only by the current overload, owing to the increased 20.
conductivity with the rise in temperature. The added surfactant
21.
elevated the current density more effectively, and conse-
quently, the onset temperature for the current overload was low 22.
compared to that of a surfactant-free system. 23.
ACKNOWLEDGMENT
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