3532 Synthetic Metals, 55-57 (1993) 3532-3537

POLYANILINE BLENDS IN THERMOPLASTICS

L.W. SHACKLETrE and C.C. HAN

Allied-Signal Inc., Research & Technology, P.O. Box 1021, Morristown, NJ 07962 (USA)

M.H. LULY
Allied-Signal Inc., Fluorine Products Division, Buffalo Research Laboratory, Buffalo, NY
14210 (USA)

ABSTRACT

The doped form of polyaniline sold under the trade name, VersiconTM, has been shown to
provide sufficient thermal stability and dispersibility for compounding with thermoplastics such as
PVC, PETG, and nylon 12 via conventional melt-processing techniques. The good performance
of polyaniline in blends derives from its thermal stability and its dispersibility as fine sub-micron
particles. Percolation curves follow a standard functional form, but the fit parameters and the
maximum achievable conductivity are a strong function of processing history and of the choice of
matrix polymer. Key Words: Polyaniline, Blends, Thermal Stability, Percolation

INTRODUCTION

The long term goal of conducting polymer development has always been to obtain a material
which would combine the convenient processibility of plastics with the electrical properties of
metals. Although melt processible conducting polymers have been known for some time [ 1,2], these
polymers could only be processed in their undoped state. Conductivity could generally be obtained
only by doping in a post fabrication step [3]. A suggestion has also been made that this drawback
could be circumvented by incorporating a dopant during molding [4], but possible deleterious
reactions between the matrix polymer and the dopant are a concern. As a further step along the
way, we and others have worked to develop conducting polymers which, although infusible, can
nevertheless be dispersed in a thermoplastic matrix to achieve a conventionally moldable or
extrudable conductive blend [5]. The major requirements for such a conducting polymer are that
it be readily dispersible in useful thermoplastic matrix polymers and that it possess thermal stability
sufficient to withstand compounding in the melt of the chosen polymer. Polymer morphology is a
major determining factor in controlling dispersibility, while thermal stability is both a function of
the chosen polymer and the particular dopant which is employed. Polyaniline is a conjugated
polymer which offers the critical combination of properties necessary for obtaining melt processible
blends in thermoplastic matrix polymers.

0379-6779/93/$6.00 © 1993- Elsevier Sequoia. All rights reserved

 3533

THERMAL STABILITY

The thermal stability of polyaniline in its neutral base form and in its emeraldine base form has
been previously studied by a number of researchers [5,6,7, and references therein]. The neutral
form of polyaniline has been shown to have very high thermal stability, being able to withstand
extended exposure to temperature in excess of 300 C. It has also been recognized that as a class,
organic sulfonic acid dopants lead to conductive compositions which also display a high degree of
thermal stability [5,6,8]. There is some difficulty, however, in comparing relative results because
there is no generally accepted procedure for evaluating thermal stability. We have built upon a
procedure which was used in the past [9] by members of our group to evaluate the thermal stability
of polyacetylene and various polythiophenes. The technique requires the monitoring of conductivity
as a function of time at a series of fixed temperatures. The conductivity is found to vary with time
according to a function of the form: a=aoexp[(t/T)a]. Once the parameters, ~ and - , are
determined at a given temperature, it is then possible to project a half-life, tl/2, for the conductivity
at that point without actually allowing the conductivity to decrease by half. Thus, the same sample
can be used to obtain data over the entire temperature range of interest. We have found that this
method gives very highly reproducible results. Finally, the conductivity half-life as a function of
temperature closely follows an Arrhenius behavior and can be used to project an expected lifetime
at any temperature.
One dopant which has been identified in the literature as leading to thermally stable compositions
of both polypyrrole and polyaniline is p-toluene sulfonic acid (PTSA) [5,6]. As an illustration of
the relative stability of polyaniline and polypyrrole, we present data in Fig. 1 for the conductivity
half-life of pressed powder samples which both contain p-toluene sulfonate anions and which were
heated in an atmosphere of flowing dry nitrogen. It can be seen that the polyaniline, in contrast
with a recently reported result [6], possesses a superior thermal stability, when such a comparison
is made on pressed powders. The projection of the curves toward long half-lives (2 5 y) suggests
that the continuous use temperature for this polyaniline tosylate composition is considerably higher
than that for polypyrrole tosylate.

10 9
10 8
10 7
10 6
to 5
10 4 [ Polyaniline Tosylate
10 a L ," ~ ' - ' i' •~ Polypyrrole,- Tosylate
to 2
101
too
lO-t
0 2'5 50 75 100 125 150 175 200 225 250 275
T e m p e r a t u r e (C)

Fig. 1. Conductivity half-life of polyaniline tosylate and polypyrrole tosylate vs temperature.

3534

DISPERSIBILITY

The form of polyaniline for which we employ the trade name, VersiconTM, is prepared as a
powder which consists of aggregates of fine particles. The aggregates consist of a basic
morphological feature which can be characterized as spheres within spheres. The average powder
grain has a dimension of about 50 I~m and consists of a collection of small spheres of about 1 am
in diameter. Upon closer examination, the one-micron spheres are themselves composed of smaller
spheres with may range in size from about 0.05 I~m to about 0.2 I~m. As we will discuss in the
following, there is evidence for yet another sub-morphological feature with a dimension of order
10 nm. These aggregates can be broken down during a conventional dispersion process to a
smallest subdividable unit, which generally consists of spheres of order 0.1 Ism (100 nm). We will
refer to this morphological unit as the primary particle. Depending on the medium in which the
VersiconTM is to be dispersed, it is usually necessary to employ both a dispersing aid and some
form of intensive mechanical mixing. The samples described in this report were first compounded
in a BrabenderTM mixer and then compression molded in a hot press.

Fig. 2. TEM micrograph of VersiconTM dispersion in PVC at 0.1 wt% loading.

Since the primary particle size is significantly less than a wavelength of visible light, dispersions
can be made in liquid media which are indistinguishable from true solutions by visual inspection.
In the case of thermoplastic media, the dispersion is made at elevated temperature in the melt of the
thermoplastic. Fig. 2 shows a dispersion of VersiconTM primary particles in a polyvinyl chloride
matrix (0.1 wt% loading) produced by Americhem, Inc. This photograph was obtained by TEM
with a ruthenium tetroxide stain. The compounding process in this case has resulted in a nearly
complete dispersion of polyaniline particles down to a primary particle size of ca. 100 - 200 nm.
It is interesting to note that the photograph offers evidence that the "primary particles" may
themselves be composed of smaller particles of order 10 nm. Other workers using scanning
tunneling microscopy have also shown that polyanilines complexed with various dopants possess a
particle-within-particle morphology where the smallest particles lie in a dimensional range of 2 - 20
 3535

TABLE 1 - Crystallinity of Polyaniline by XRD

23 ° Peak 43 ° Peak
Versicon Sample CI (%) CSP (A) CSP (A)

PP#55 30 71.9 35.4

PP#57 36 70.0 35.4
PP#58 34 69.2 35.4
CI is the crystalline index (relates to % crystallinity)
CSP is the crystallite size and perfection (relates to crystallite size)

nm [10]. X-ray diffraction analysis (Table 1) reveals a crystallite size (7 nm) which is
commensurate with the smallest structures observable in TEM and STM.
The PVC blend in Fig. 2 also illustrates another key property of polyaniline, the tendency for the
conductive particles to reaggregate in the molded article as long chains. This spontaneous
condensation of particles contributes to the formation of conductive pathways in the otherwise
insulating matrix at comparatively low loading levels of polyaniline. The critical concentration of
the conductive filler necessary to achieve this percolation is defined as the percolation point and is
generally expressed as a critical volume fraction (q~c). The phenomenon is illustrated by graphing
the logarithm of conductivity versus volume percent loading as depicted in Fig. 3. The curves in
this plot were obtained by a nonlinear regression fit to a function of the form, o = ao(q~ - q~e)t,
derived from random percolation theory. This relation applies only near the percolation point for
> q~c- The theoretical model for a random lattice of spheres predicts a q~c which lies in a range
from about 0.15 to 0.30 depending on the sphere diameter (hard core size) [11].

101
10 0
lO-I
10-2
2 10-3
10-4 * Versicon/PCL
• Versicon/PETG
10-5
O
L9
10-6
10-7
lO-a I , , ,

4 8 12 16 20 24 28 32 36 40
V o l u m e F r a c t i o n of V e r s i c o n TM (~)

Fig. 3. Percolation behavior of Versicon TM above the critical volume concentration.

3536

TABLE 2 - Percolation above the Critical Concentration

~0¢ oo t

Random Filling (3D) 0.15 - 0.30 1.6 - 2

PAni in PETG 0.062 93 2.8

PAni in PCL 0.046 292 1.9

The results of this work are clearly matrix dependent, since the percolation behavior is found to
be different for the two matrix polymers, polycaprolactone (PCL) and poly(ethyleneterethphalate
glycol) (PETG). The parameter, %, is akin to an intrinsic conductivity of the filler, i.e., the
conductivity that would be measured for the individual polyaniline particles by themselves. The
value determined for Oo, however, can be both matrix and process dependent. Nevertheless, a value
in a range of 100 to 300 S/cm is consistent with values measured for pure oriented samples of
polyaniline. By any estimate, it is clear that the conductivity of the polyaniline primary particles
is considerably greater than the value normally quoted for unoriented bulk polyaniline (1 to 20
S/cm), since the conductivity measure for the PCL blend is already greater than 20 S/cm at a
loading of only 33 vol%. The value of the exponent, t, is generally thought to be universal and
both theoretical predictions and many experimental systems display a value near 2 [12].
The tendency of the conductive polyaniline particles to aggregate in the matrix leads in both cases
to a critical volume fraction, ~e, which is significantly below that which would be expected if the
polyaniline particles were randomly distributed. At some point during the processing and molding
of the blends, the dispersed polyaniline particles partially reaggregate. This process occurs because
the polyaniline is not compatible with the matrix polymers employed here. This incompatibility can
be described in various terms as for instance a mismatch in surface energy or a mismatch in
solubility parameter. The appearance of one- and two-dimensional condensed structures lacks a
detailed explanation; however, one possible explanation may lie with the surface energy mismatch
causing the polyaniline particles to be driven from regions of the melt. In the absence of shear and
strain fields such a process would cause the exclusion of conductive particles from roughly spherical
domains. These conductive particles would then collect at the periphery of such domains, forming
one- and two-dimensional aggregated structures, like those in evidence in Fig. 2. Such a
distribution of conductive particles has been demonstrated to lead to dramatically lower critical
volume fractions in other phase-separated systems where the average dimension of insulating
domains is much larger than the corresponding dimension of the conductive particles [13]. This
argument suggests that the excellent percolation results obtained here stem directly from the small
primary particle size which is characteristic of most forms of polyaniline. Observations with
carbon-black filled composites also support a relationship between particle size and critical volume
fraction [14]. The remaining key technology demonstrated here with VersiconTM is the ability to
disperse aggregates of the material down to the level of the primary particle.

CONCLUSIONS

Polyanilines with selected thermally stable dopants have been shown to possess sufficient thermal
stability and dispersibility to form highly conductive blends in thermoplastics such as PVC, PETG,
and PCL. Such blends in nylon and poly(vinyl chloride) (PVC) have been shown elsewhere to be
highly effective as moldable and/or extrudable electromagnetic shielding materials [15].
 3537

ACKNOWLEDGEMENTS

We take special pleasure in acknowledging the vital contributions of V.G. Kulkarni of

Americhem, Cuyahoga Falls, OH in preparing the PVC blends and B. Wessling of Zipperling
Kessler, Ahrensburg, FRG for developing the techniques for blending polyaniline in thermoplastics
such as PETG and PCL. Would also like to thank V. Kramer and N.S. Murthy of Allied-Signal
for obtaining the TEM and XRD data, respectively.

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