POLYMER
JOURNAL
www.elsevier.com/locate/europolj
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).
0014-3057/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2007.06.046
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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-
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(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.
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.
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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.
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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)
(a)
(Log) (S.cm-1)
-2
(b)
-4
-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
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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.
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