EUROPEAN

POLYMER
JOURNAL

European Polymer Journal 43 (2007) 45654572

www.elsevier.com/locate/europolj

Polyaniline/thermoplastic polyurethane blends: Preparation

and evaluation of electrical conductivity
Denice S. Vicentini a, Guilherme M.O. Barra
Alfredo T.N. Pires b

a,*

, Jose R. Bertolino b,

Mechanical Engineering Department, LABMat, Federal University of Santa Catarina, Campus Universitario,
88040-900 Florianopolis, Santa Catarina, Brazil
Chemistry Department, POLIMAT, Federal University of Santa Catarina, Campus Universitario, 88040-900 Florianopolis,
Santa Catarina, Brazil
Received 3 October 2006; received in revised form 14 May 2007; accepted 29 June 2007
Available online 18 July 2007

Abstract
Conducting polymer blends whose undiluted components have dierent properties are promising materials for specic applications and have attracted interest in recent years. The aim of this study was to obtain and evaluate the electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA)/polyurethane thermoplastic
(TPU) blends. The PAni.DBSA was synthesized from DBSA-aniline (DBSAn) salt through an emulsion polymerization
in tetrahydrofurane (THF) or in the presence of polyurethane thermoplastic solution, resulting in pure PAni.DBSA or
PAni.DBSA/TPU blends. Blends of PAni.DBSA/TPU were also prepared through casting, at room temperature, after
dissolving both components in THF as a common solvent. The insulatorconductor transition was very sharp and the
percolation threshold was lower than 2.7 wt% of PAni.DBSA. The electrical conductivity of PAni.DBSA/TPU blends,
prepared by both methods, reached maximum values at a PAni.DBSA concentration of 40 wt%, close to the value
observed for the undiluted conducting polymer. However, for a PAni.DBSA content lower than 30 wt%, the electrical
conductivity was dependent on the blend preparation method. Blends were characterized by infrared spectroscopy, thermogravimetric analysis (TG) and optical microscopy. The electrical conducting characteristics of the PAni.DBSA/TPU
blends prepared using dierent procedures indicate a high potential for their successful application in electrical
processes.
 2007 Elsevier Ltd. All rights reserved.
Keywords: Polyurethane thermoplastic elastomer; Polyaniline; Electrical conductivity

1. Introduction

*
Corresponding author. Tel.: +55 48 37219387; fax: +55 48
37217615.
E-mail address: guiga@emc.ufsc.br (G.M.O. Barra).

Intrinsically Conducting Polymer (ICPs) are

promising materials for various applications.
Polyaniline (PAni) is a conducting polymer which
has been extensively studied due to its environmental stability and simple methods of synthesis.

0014-3057/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2007.06.046

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Unfortunately, the poor processability of PAni and

its inadequate mechanical properties limit its commercial applications. In order to overcome these
problems, numerous methods have been studied
[1,2].
Techniques based on the dispersion of conducting polymer particles in a matrix comprised of common insulation polymers have been receiving
increasing attention and are very attractive due to
the possibility of combining the good processability
and mechanical performance of the conventional
polymer with the electrical and optical properties
of PAni. However, polyaniline is usually immiscible
when blended with other polymers, and a phase separation process restricts the formation of more integrated materials. If the compatibility of these blends
were enhanced then the electrical properties would
potentially increase. Less phase separated blends
lead to materials with enhanced mechanical and
electrical properties. Methods to improve compatibility in conducting polymer blends include the use
of compatibilizers such as block copolymers or ionic
polymers [35]. Another way to increase compatibility is to insert counter ions, such a functionalized
protonic acids, between the polyaniline (PAni)
chains making it possible to form blends with a conventional polymer. An example of such a functionalized acid is dodecylbenzenesulfonic acid (DBSA),
which has long alkyl chains that increase the solubility of PAni.DBSA in toluene, xylene, etc., and acts
as a surfactant, inducing compatibility with polymer
matrices with a similar structure [6]. These blends
are normally obtained by mixing soluble or fusible
polyaniline with other polymers in solutions or
melts [710]. Blending of PAni with conventional
polymers through solution processing has been
reported to be ecient when both polymers are soluble in a common solvent.
The in situ emulsion polymerization of aniline
(Ani) in the presence of a host insulation polymer is
an interesting route through which more compatible
conducting blends can be obtained. In this method,
the oxidative polymerization of aniline is carried out
by introducing an aqueous solution of an oxidant
(ammonium persulfate) into an organic emulsion
of the host polymer, aniline and a protonation
agent. The blends are obtained by subsequent coprecipitation of the PAni and the host polymer.
The use of a thermoplastic elastomer with conducting polymers is very attractive due to the combination of mechanical properties and a
processability which does not require vulcanization.

Thermoplastic polyurethane (TPU) is one of the

most versatile products in the group of engineering
thermoplastics with elastomeric properties. TPU is
characterized by a two-phase morphology in which
a soft phase containing either polyesters or polyethers is reinforced by condensation with a hard
domain consisting of an aromatic diisocyanate
extended with a short-chain diol. The excellent
physical properties, chemical resistance and abrasion resistance of TPU, as well as its ease of processing, make it of interest to blend TPU with other
polymers, such as polyaniline. Several conducting
polymer blends have been prepared by in situ
emulsion polymerization of aniline in the presence
of a thermoplastic elastomer [1116], but none of
these preparations employed thermoplastic polyurethane as the host matrix.
This study investigated the inuence of the blend
preparation method on the electrical conductivity
and morphology of the blend. To this aim, we prepared PAni.DBSA/TPU blends through two methods, solution casting and in situ emulsion
polymerization.
2. Experimental
2.1. Materials
Aniline (Ani) (analytical grade, Merck) was distilled twice under vacuum and stored under nitrogen
with cooling. Ammonium peroxydisulfate (APS)
(analytical grade, Merck) and dodecylbenzenesulfonic acid (DBSA) (technical grade, Pro-Quimica
do Brasil) were used without further purication.
The thermoplastic polyurethane (TPU Desmopan
385 ester based) was kindly supplied by Bayer.
The dodecylbenzenesulfonic acid aniline salt
(DBSAn) was prepared by mixing DBSA and aniline, with a stoichiometric ratio of the chemical reaction as shown in Scheme 1. DBSAn was
recrystallized with water and methanol before
polymerization.
2.2. Synthesis of PAni.DBSA
The polymerization of aniline salt was performed
by adapting a procedure described in the literature
[17,18]. DBSAn (0.01 mol) was dispersed in 60 mL
of THF under stirring, at 5 C, and 0.005 mol of
ammonium persulfate (APS) aqueous solution was
slowly added. The polymerization reaction was
maintained for at least 6 h, and the product was then

D.S. Vicentini et al. / European Polymer Journal 43 (2007) 45654572

4567

Scheme 1.

precipitated in ketone. The dark green powder precipitate was ltered, washed with water and dried
under vacuum at room temperature.
2.3. Blend preparation
PAni.DBSA/TPU blends were prepared using
two dierent methods: (i) the polymers were dissolved in a common solvent (THF), stirred for 3 h
and the solution was cast on a glass plate to evaporate the solvent at room temperature, obtaining
lms with specic thickness, and (ii) 0.01 mol of
DBSAn and 115 g of TPU dissolved in THF were
added to an aqueous solution of 0.005 mol of
ammonium persulfate. The reaction was carried
out at 5 C for 6 h. Samples were then precipitated
in ketone and washed several times with water to
remove unreacted monomers. All samples were
dried in a drying chamber under vacuum before
analysis.
2.4. Characterization
The electrical conductivity of the blend lms,
with 100200 lm thickness (method i), and specimens prepared by compression molding at 100 C
for 5 min (method ii) were measured using a Keithley electrometer 614 and a Keithley power source
224. The four-probe method was used where an
electrical current is applied between the external terminals and a voltage is measured between the two
internal terminals.
The UVvis spectra of pure PAni were obtained
on a Perkin Elmer, Lambda 11, UVvis
spectrometer.
Infrared spectroscopy (FTIR) was performed
with a Perkin-Elmer, model 16 PC, instrument with
a resolution setting of 4 cm1, to obtain spectra of
pure TPU, PAni.DBSA and blends. The spectra
were tted to evaluate the real contribution of each
component, using Origin 7.0 software and Gaussian
bases.
The morphology of the lm surfaces was analyzed using a Leica DM LM microscope, with a
50 or 100 magnication.
Thermal analysis was carried out using a TGA 50
Shimadzu thermogravimetric analyzer. Non-iso-

thermal experiments were performed at 10 C min1

from 25 to 800 C. The nitrogen ow was maintained at 50 cm3 min1. Before the analysis, the
samples were dried in a drying chamber under vacuum at room temperature for 48 h.
3. Results and discussion
3.1. Characteristics of Pani.DBSA samples used in
the blends
The emulsion polymerization of dodecylbenzenesulfonic acid aniline salt (DBSAn) in an organic
medium, such as chloroform, toluene, and other solvents [17], opened new possibilities for the preparation of conducting blends via a one-step in situ
method. Considering that THF is the common solvent for PAni.DBSA and TPU, it was used in this
study as an organic medium in the emulsion polymerization of DBSAn with the aim of obtaining
conducting PAni.DBSA/TPU blends through
in situ or solution casting processes. Firstly, the
synthesis conditions required to obtain an appropriate electrical conductivity and yield of PAni.DBSA,
with THF as the solvent, were investigated.
An optimum conductivity is reached when two
nitrogen atoms per repeating PAni unit are protonated, which corresponds to half the number of nitrogen atoms in the macromolecular chain. By treating
PAni.DBSA with ammonium hydroxide, it becomes
deprotonated and the emeraldine base (PAni) is
obtained. This type of PAni is non conducting, the
conductivity level being of the order of
1010 S cm1. The emeraldine base could be evaluated by the UVvis spectrum, with two characteristic absorption bands at 330 and 630 nm, attributed
to the pp* transition of the benzenoid rings and
the absorption of the quinoid rings, respectively.
The UVvis spectrum of PAni.DBSA after treating
with base solution is shown in Fig. 1, identifying the
emeraldine base. For the conducting form
(PAni.DBSA), the UVvis spectrum shows a characteristic polaron band at 350450 nm, which is
related to the pp* transition. A second absorption
band at 750 nm is attributed to the polarons formed
from the protonation of the imine groups of the
polymer chain. The disappearance of the absorption

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D.S. Vicentini et al. / European Polymer Journal 43 (2007) 45654572

774 nm
0.5

(b)

Absorbance

0.4

630 nm
(a)

0.3

0.2

0.1

300

400

500

600

700

800

900

(nm)

Fig. 1. UVvis spectra for (a) PAni emeraldine base and (b)
PAni.DBSA sample.

at around 630 nm suggests protonation of the imine

nitrogen atoms by DBSA molecules. Through the
method described in the experimental section, an
emeraldine salt with a yield of 12% and an electrical
conductivity of 0.5 S cm1 was obtained.
3.2. Blend characterization
Infrared spectroscopy is an important tool used
to characterize the interactions between two or
more components in a polymer blend. It has been
reported that the carbonyl and amine functional
groups are operative in mixtures of polyurethane
and polyaniline [19].
The infrared spectra of PAni.DBSA, TPU and
PAni.DBSA/TPU blends are shown in Fig. 2. The
absorption bands in the region of 3330 and
(a)

Absorbance

(b)
(c)
(d)
(e
(f)
4000

3500

3000

2500

2000

1500

1000

500

Wavenumber (cm-1)

Fig. 2. FTIR spectra for (a) TPU (b) PAni.DBSA, (c) and (d)
PAni.DBSA/TPU blend obtained through in situ process, (e)
and (f) PAni.DBSA/TPU blend obtained through solution
casting process at 50/50 and 30/70 w/w, respectively.

3250 cm1 are consistent with the NH absorption

bands corresponding to TPU and Pani.DBSA,
respectively. In the case of the infrared spectrum
for TPU, there are two distinct bands that overlap
extensively at 1735 and 1704 cm1 relating to carbonyl absorption. The free carbonyl absorption
in undiluted TPU is asymmetric and gives an infrared peak at 1735 cm1 and the low wavenumber
peak at 1704 cm1 is representative of the carbonyl
absorption which is perturbed by hydrogen-bonding
of the parent molecules.
The infrared spectrum of PAni.DBSA showed
two absorption bands at 1585 and 1498 cm1 corresponding to quinoid and benzenoid ring deformations, respectively, which is in good agreement
with the characteristic bands of emeraldine salt
reported in the literature (Fig. 2b) [20]. In the
regions of 1305 and 829 cm1 the CN stretching
of the secondary aromatic amine and an aromatic
CH out of plane bending modes, respectively, are
observed. In addition, the 1139 cm1 band is attributed to the stretching vibrations of the sulfonic
group (S@O).
Fig. 3 shows infrared spectra with Gaussian
deconvolution in the range 1800 to 1650 cm1 for
(a) TPU; (b) and (c) PAni.DBSA/TPU blend prepared by in situ process at 30/70 and 50/
50 wt%, respectively; (d) and (e) PAni.DBSA/TPU
blend prepared by solution casting at 30/70 and
50/50 wt%, respectively, which corresponds to the
free and site-specic interactions between the carbonyl and amine groups. The free carbonyl absorption in the undiluted TPU becomes less pronounced
when the concentration of PAni.DBSA increases for
blends prepared by the in situ process. These
results provide direct support for the fact that sitespecic interaction between the NH and C@O
functional groups are operative in mixtures of
PAni.DBSA and TPU. These data also reveal that
there are considerable fractions of both free and
bonded carbonyl amine groups even when TPU is
the dominant component at a concentration of
70 wt% as illustrated in Fig. 3b. For 50 wt% of
TPU, only one peak at 1704 cm1 was observed,
which indicates that a lower number of free carbonyl groups is present. On the other hand, blends
prepared by solution casting (Fig. 3d and e) show
a very wide vibration band in 1720 cm1, which
could be attributed to the presence of free and
bonded carbonyl groups, but with less site-specic
interaction of functional groups than blends prepared by the in situ process.

D.S. Vicentini et al. / European Polymer Journal 43 (2007) 45654572

4569

1800

Absorbance

Absorbance

1780

1760

1740

1720

1700

1680

1660

1800

1780 1760

1740

1720

1700 1680

1660

Wavenumber (cm-1)

1800

Absorbance

Absorbance

1780

1760

1740

1720

1700

1680

1800

1660

1780 1760

1740

1720 1700

1680

1660

Wavenumber (cm-1)

Wavenumber (cm-1)

Absorbance

1800 1780

1760

1740

1720 1700

1680

1660

Wavenumber (cm-1)

Fig. 3. Infrared spectra with Gaussian deconvolution in the range 18001650 cm1 of (a) TPU, (b) and (c) PAni.DBSA/TPU blend
prepared through in situ process (d) and (e) PAni.DBSA/TPU blend prepared through solution casting at 30/70 and 50/50 w/w,
respectively.

The value for the solid residue of the PAni.

DBSA/TPU blend prepared by solution casting at
30/70 w/w, calculated from thermogravimetric
curves of undiluted components, was 38%, which is
in agreement with the experimental value, as shown
in Fig. 4. As expected, the composition of the nal
blend prepared through the solution casting process
corresponds the quantity of each component added.
However, on using the same initial composition of

components to prepare blends through the

in situ process, there was a lower amount of solid
residue (around 6% less) due to the washing step
required to eliminate the monomeric units that had
not reacted during the polymerization step. The
blends are thermally stable at 200 C.
The blends prepared by the solution casting and
in situ process show a very sharp insulatorconductor transition and electrical conductivity values

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D.S. Vicentini et al. / European Polymer Journal 43 (2007) 45654572

sented in Fig. 5 can be tted to the scaling law of

percolation theory [21,22], as described in Eq. (1):

100

rf cf  fp

Weight (%)

80

60

(a)
(b)
(c)

40

20

(d)
0
0

100

200

300

400

500

600

700

800

Temperature (oC)

Fig. 4. Thermogravimetric curves for (a) undiluted TPU, (b) and

(c) PAni.DBSA/TPU blend obtained through solution casting
and in situ process, respectively, at 30/70 w/w and (d)
undiluted PAni.DBSA.

increased with increasing PAni.DBSA content, as

illustrated in Fig. 5. The electrical conductivity
value for undiluted PAni.DBSA is close to that
for samples with 40 wt% of this component in the
mixture, for both blend preparation methods.
Below this concentration the curves show the same
trend, with an approximately 10-fold dierence in
electrical conductivity values in the range of 20
40 wt% of PAni.DBSA. This behavior suggests that
the formation of interconnected conducting
PAni.DBSA grains inside the TPU can be aected
by the blend preparation procedure. These results
are consistent with the morphological features of
the blends, as it will be discussed later. The data pre-

(a)

(Log) (S.cm-1)

-2

(b)

-4

where c is a constant, t a critical exponent, rf the

conductivity, f the fraction of the conductive medium and fp the fraction at the percolation threshold,
expressed in a weight fraction.
The percolation threshold and others parameters
calculated through the plot of log r versus log (ffp)
are showed in Table 1. The values for the critical
exponent were in the range of 24, which can be
explained by multiple percolation in conducting
polymer blends, as proposed by Levon and Margolina [21]. These authors suggest that the conductivity depends on the blend preparation method,
rather than simply on the conducting polymer content. The low fp value for the PAni.DBSA grains in
the TPU matrix probably reects a high
PAni.DBSA/TPU compatibility in the blends, due
to the presence of the carboxyl/amine group
interaction.
The eect of the PAni.DBSA addition on the morphology of the TPU blends was evaluated by optical
microscopy. Fig. 6 shows the micrographs of
PAni.DBSA/TPU blends at 15/85 and 30/70 wt%,
where the dark regions correspond to the disperse
PAni.DBSA phase. The microstructure of the
PAni.DBSA/TPU blends revealed typical phase separation with the presence of conducting polymer aggregates. The conductivity value of 1.7 106 S cm1 for
casting blends at 15 wt% PAni.DBSA content is in
agreement with the morphology shown in the micrograph of Fig. 6a, which indicates a low level of conducting pathways. On increasing the amount of
conducting polymer in the TPU matrix, the disperse
phase is better interconnected resulting in high electrical conductivity (Fig. 6c). When the PAni.DBSA content was doubled, the electrical conductivity value was
1.5 102 S cm1, which signies approximately a
10,000-fold increase.

-6
-8

Table 1
Percolation threshold data of PAni.DBSA/TPU prepared by
solution casting and in situ methods

-10
-12
0

20

40

60

80

Preparation
Method

Percolation
threshold (fp)
(wt%)

Critical
exponent
(t)

Correlation
coecient (R)

Solution
casting
in situ

2.7

3.7

0.98

2.0

4.2

0.99

100

PAni.DBSA content (wt%)

Fig. 5. Electrical conductivity of blend prepared through (a)

in situ and (b) solution casting process.

D.S. Vicentini et al. / European Polymer Journal 43 (2007) 45654572

4571

Fig. 6. Micrographs of the PAni.DBSA/TPU blends prepared through (a) and (c) solution casting, (b) and (d) in situ process at 15/85
and 30/70 w/w, respectively.

However, the PAni.DBSA/TPU blends prepared

using the in situ process showed dierent morphological characteristics at the same blend compositions as those obtained by casting. In the
micrographs of Fig. 6b and d the interconnected
phase for both blend compositions can be observed.
For this preparation process, the electrical conductivities were 6.9 105 and 1.2 101 S cm1 for
15/85 and 30/70, respectively, approximately 10
times higher than the values observed for the cast
blends. The morphology characteristics explain the
lower percolation threshold and higher electrical
conductivity for the PAni.DBSA/TPU blends
obtained through the in situ, compared to the
solution casting process.
Yoshikawa and coworkers [23] prepared PAni/
PU through solution casting blends in tetrahydrofuran and they obtained electrical conductivities of
5 1012, 3 107 and 1 105 for volume fraction
percentages of PAni of 5, 10 and 30, respectively. In
the case of a lower PAni content (<15 vol%), the

electrical conductivity values are in the same order

of magnitude as the blends obtained through solution casting in this study. However, for all components of the blend composition prepared using the
in situ process, electrical conductivity was higher.
Another interesting result, present by Yoshikawa
and coworkers, is that carbon black/PU composites
prepared in THF by mixing in a mortar, had dierent conductivity values as a function of the volume
fraction of the conducting components, the values
being comparable with PAni/PU blends.
4. Conclusions
Conducting PAni.DBSA/TPU free-standing
lms can be obtained by solution casting or
in situ methods. TPU was immiscible with
PAni.DBSA, resulting in a gross-phase separation
in the blends with a low electrical conductivity prepared through the casting process. The dierent
methods used to prepare the PAni.DBSA/TPU

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D.S. Vicentini et al. / European Polymer Journal 43 (2007) 45654572

blends signicantly aected the conductivity values

and percolation threshold. The in situ blend preparation method was able to produce PAni.DBSA/
TPU blends with enhanced compatibility, resulting
in a ne dispersion and ne conducting pathways.
The results revealed that the extent of the conducting polymer dispersion in the isolating polymer
matrix exerts a strong inuence on the electrical
properties. The dispersion is favored by the solubility of the isolating matrix in the common solvent
and also by the blend preparation method.
Acknowledgement
The authors would like to thank CAPES for the
nancial support.
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