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ELSEVIER Synthetic Metals 102 (1999) 1163-l 166

Conducting Polymers and Their Applications in The Film Industry

--- Polyaniline/Polyimide Blended Films

Gary Min
Du Pont Circleville Research Laboratory, Circleville, OH 43 113 (U.S.A)

I. Abstract
Conducting polymers have been widely investigated for both academic and industrial purposes over two decades.
Their attractive electrical and optical properties provide a lot of potential applications in the film industry. However,
their poor mechanical properties and instability limit some industry applications. Thus, considerable attention has
been given to produce polyaniline/polyimide blended films by a solution blending technique. The percolation levels
of the polymer blended system were studied and their film morphology and properties were well characterized by
various instruments such as TFM, INSTRON, and X-ray diffractometer. The excellent film properties have
generated great interest in several industry applications.
Keywords: Polyaniline, Polyimide, Polymer blended film

II. Introduction B. Polyimides

A. Intrinsic Conducting Polymers Aromatic polyimides with outstanding thermal,
mechanical, electrical, and solvent resistance
An intrinsically conducting polymer (ICP), more properties have been widely used in the electronic
commonly known as a “synthetic metal,” is an industry, aerospace, automobiles, wire insulating, and
organic polymer that possesses the electrical, high performance parts. In general, there are two
electronic, magnetic and optical properties of a metal types of polyimide materials, i.e., heat-sealable and
while retaining the mechanical properties, solubility, non-heat-sealable. For example, the well known
processibility, etc., commonly associated with a Kapton@H film[2], that is obtained by the
conventional polymer [l]. These properties are condensation of pyromellitic dianhydride (PMDA) and
intrinsic to the doped material. This class of polymer oxydimethyl aniline (ODA), is a non-heat-sealable
is completely different from “mixed conducting material and its chemical structure is shown in Figure-
polymers” which are merely a physical mixture of a 1.
non-conductive polymer with a conducting material
such as metal or carbon powder. They are
synthesized by “doping” an organic polymer, either
an insulator or semiconductor, having a low
conductivity, typically in the range lo-l5 to 10m5
S/cm, to a material which is in the “metallic”
conducting range (-1 to lo4 S/cm) or semiconductive
range ( 10m6 to loo S/cm). At the present time
polyaniline is without doubt the most important
conducting polymer from the point of view of large Figure- 1. Chemical stmcture of PMDA//ODA non-
scale technological use. However, other conducting heat-sealable polyimide.
polymers such as, polythiophene,
poly(phenylenevinylene), polypyrrole, polyacetylene,
and polyparaphenylene show considerable The other type is heat-sealable polyimides such as
technological promise as specialty polymers. Kapton@-KJ, LJ, JP films [3]. Normally, the heat-
sealable polyimides contain repeating imide units
derived from 4,4’-oxydiphthalic dianhydride and an

0379-6779/99/$ - see front matter 0 1999 Elsevier Science S.A. All rights reserved.
PII: SO379-6779(98)00375-O
1164 G. Min / Synthetic
aromatic ether diamine of the formula as shown in
Figure-2a and from additional repeating imide units
derived from a tetravalent aromatic carboxylic
dianhydride and a divalent aliphatic or aromatic
diamine of the formula as shown in Figure-2b. The
heat-sealable polyimide provides adhesion to various
metal and plastic substrates.
Figure-2a. An aromatic ether diamine.
r 0II I: 1 processing.
Figure-2b. Repeating imide units derived from a
tetravalent aromatic carboxylic dianhydride and a
divalent aliphatic or aromatic diamine.
III. Solution Blended Polyimide Films
Both conducting polymers and high performance
polymers have been widely investigated individually
for several decades. The resultant synergy from
blending these types of polymer overcomes the poor
mechanical properties and instability of the
conducting polymers. Some work was published
using conducting polymers blended with
conventional polymers, such as, polyvinylchloride,
Nylons, and PMMA [4] for use in electromagnetic
interference shielding. However, a few publications
mentioned the use of high performance polymers,
such as, polyimide, poly(ether ether ketone),
polysulfone, and poly(amide imide) due to their
critical processing conditions [5]. In this paper, we
would like to introduce the concept of a
polyaniline/polyimide blended film from the use of
solution blending techniques.
A. Experimental Processing
There are several ways to blend polyaniline and
polyimides. The solution blending method is more
comparable to current polyimide film processing
techniques since both polyaniline and the polyamic
acid precursor are co-soluble in some polar organic
solvents such as N,N-Dimethylacetamid @MAC),
Dimethyl sulfone (DMSO), N,N-Dimethylformamide
(DMF) and N-methylpyrrolidinone (NMP), et al. A
Metals 102 (1999) 1163-1166
laboratory method can be used to make polyaniline
/polyimide blended films. A certain concentration of
polyaniline solution and polyamic acid precursor
solution were prepared in advance and blended
homogeneously. The blended solution was then cast
on glass substrates and dried at 90°C for about one
hour. The pre-dried blended film was placed in an
oven at 150°C for 30 minutes and then 350°C for 10
minutes to complete the imidization of polyimide as
shown in Figure-3. The blended film was then
“doped” in -5 M HCl solution to give the
conductivity. However, industrial scale-up
processing will require some additives to prevent
polymer solution gelling. In addition, different types
of polyaniline dopants [6] can be added during the
0R 0 +H2N~O~NH2
90d 'f ODA
ImAo
+ Polar Organic Solvent
1
Polvamic Acid Precusor
4+ -Dolvaniline Solutioq
Polvaniline/PolvamicAcid Mixture
Casting and Curing
Polvaniline/Polvimide Blended Film
Figure-3. A laboratory method to make
polyaniline/polyimide blended film. The dashed lines
between polymers represent probable interactions
between the polyamic acid and polyaniline[5].
 G. Min I Synthetic Metals 102 (1999) 1163-1166 1165

B. hlorphotogy and Structure Studies C. Etcctricat tlntt Mcch;lnid Prop-ties

The TEM picture of the cross-section of
pol~nnilinelpolpimide blended film (15 wt.% of
pal? aniline) as sho\vn in Figure-4 indicated some Thin polya’ulincipol~iniidc blended films (3-20 ttm)
pol!.mcr-polymer interpenetrating network (IPN) 1va.s were “doped” at 5.0 M of HCl solution for about 72
formed bet\\een polyimide and polyaniline. The X- hours and then the film was dried under vacu~~~~~ for
rq study indicated a amorphous stn’cture [7] of the about 24 hours to remove the excess HCl. Their
pol~a’&e/polyimide blended film as shown in volume rcsistivities were listed in Figure-6. Actually,
Figure-5. there arc some probable interactions between the
polyamic acid and polyaniline as shown in Figure-3
(schematic dashed line). Since the polyamic acid is a
weak acid, the major contribution of the “doping” is
coming from the strong acid, “HCl”. For example,
the resistivity of the non-HCl “doped“ blended film is
in the range of 10’ 4 - 10’ 6 R*Cm which are
insulating materials

16
@Volume Resistivit)

0
Figure-a. TEM of the cross-section of
polyaniline/polyimide blended film under 50,000
magnification.
0

0
l
0

pure Polyimide
0
0 5 10 15 20 25 30
5% polyanitine
Polyaniline Loading (wt.%)
10% polyaniline
Figure-6. Volume resistivity of polyaniline
15% polyaniline /polyimide blended films

20% polyaniline
The mechanical properties of the blended films were
30% polyaniline measured by using a Instron machine and the results
arc shown in Figure-7. Unespectly. The tensile
strength of 15% by weight of polyaniline blended
Pure polyaruline film were even higher than the control (pure
+-
5 10 15 20 25 30 35 polyimide film). This could be added e\,idence of
20 forming a polymer interpenetrating net\vork betjveen
the polyimide and polyaniline.
Figure-5. The X-ran spcctn’m of the
polyaniline/polq-in;de blended film.
1166 G. Min I Synthetic Metals 102 (1999) 1163-1166

80 ‘1919 Those excellent film properties indicated some

, l Tensile strength potential applications in gas separation membranes,

2-I 60
2 60-
70.'
70
P 0 Elongation

0
0
00 -18 .z

2
resistors, EMI shielding, and filtration applications.
Not only polyaniline can be blended with polyimide;
some other conducting polymers such as
polyparaphenylene , polythiophene, polypyrrole, and
V 0o poly(phenylenevinylene) can also be used to blend
fz
fz
‘fi
00
0
-17
9 with polyimides which will expand the application
‘fi2 50 0 ranges. For example, a derivatives of polythiophene
2 50- t!i
8 0 0 -16 2 blended polyimide film is a light green colored
40.'
40 2 transparent film with a volume resistivity of lo2
00 0Cm which should be of interest to make a
I G
l-
0 915 conducted electrode for LED displays.
30. 0 0 915
.
0 (P

0 5 10 15 20 25 30 IV. Summary:
Polyaniline Loading (wt.%)
Free-standing polyaniline/polyimide blended thin
films were successfully prepared from mixing
solutions of polyaniline and polyamic acid precursor
Figure-7. Mechanical properties of polyaniline of both heat-sealable and non-heat-sealable types.
/polyimide blended films The morphology and structure were characterized by
TEM and X-ray diffraction. Their excellent electrical
and mechanical properties indicated some potential
application should be found in gas separation
membranes, resistor films, EM1 shielding materials,
D. Technical Data Sheet and for filtration.

Some technical data of polyaniline blended with both

heat-sealable and non-heat-sealable nolvimide were
listed in Table-l. V. References

Table-l. Technical Data Sheet: [l]. W.S. Huang, B.D. Humphrey and A.G.
MacDiarmid, J. Chem. Sot.. Faradav Trans. I. 82,
Properties Non-Heat- 1 Heat- I 1986,2385.
I sealable
~polyimide 1 E?$!de 1 [2]. C,.E. Sroog, ,I. Polvm. Sci. -01. Rev.. 11
1976,179.
[3]. Kanakarajan et al, U.S. Patent 5,298,33 1, March
29,1994.
[4]. Hexel Company, Press Release, November,
1989; Allied Signal-Americhem-Zipperling, Press
Release, May 199 1.
[5]. TimM. Su et al, &r&hMet.. 84, 1997, 801-802.

I Volume Resistivity
Log(Q*Cm) [6]. Y. Min, Y. Xia, A.G. MacDiarmid,
Epstein, Spnth Met.. 69, 1995, 159.
and A.J.

I Melting Point (‘C) I

None
I
280
I [7]. A.G. MacDiarmid, Y. Min, J.M. Wiesinger, E. J.
OH, E.M. Scherr, and A.J. Epstein, Svnth Met. 51 -
-140
Glass Tran. Temp. (‘C) None a., 1991,977.