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Synthetic Metals 158 (2008) 104–107

Production of polypyrrole fibres by wet spinning

Javad Foroughi, Geoffrey M. Spinks,
Gordon G. Wallace ∗ , Philip G. Whitten
ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute,
University of Wollongong, Northfields Avenue, Wollongong, NSW 2522, Australia
Received 17 August 2007; received in revised form 12 October 2007; accepted 10 December 2007
Available online 19 February 2008

Abstract
Soluble, doped polypyrrole containing no substituent on the pyrrole ring has been synthesized by the incorporation of the di-(2-ethylhexyl)
sulfosuccinate dopant anion, which renders the polymer soluble in various organic solvents. The solutions were amenable to a wet-spinning
process that produced continuous doped polypyrrole fibres. The ultimate tensile strength, elastic modulus and elongation at break of the obtained
fibres were 25 MPa, 1.5 GPa and 2%, respectively, with an electronic conductivity of ∼3 S/cm. Cyclic voltammetry demonstrated the electroactivity
of the polypyrrole fibres. These fibres are likely to be important for electronic textile applications.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Polypyrrole; Fibre; Wet spinning; Conducting polymer; Electronic textile

1. Introduction mon organic solvents such as chloroform and tetrahydrofuran

Polypyrrole (PPy) manufactured by conventional chemical
and electrochemical methods is normally insoluble in ordinary
organic solvents [1,2] and this intractability has been attributed
to the presence of strong interchain interactions [3]. Conse-
quently, PPy films are normally prepared electrochemically with
the size of the film restricted to the electrode area, although, slow
production of PPy tape has been demonstrated using a rotating
anode apparatus [4]. In contrast, other conducting polymers like
polyaniline and polythiophene can be prepared in solution and
this is subsequently amenable to solution casting, printing or
even fibre spinning [5]. The latter is preferred in the preparation
of large quantities of fibres for electronic textile applications.
This paper reports, for the first time, the preparation of wet-
spun polypyrrole fibres using recently developed soluble PPy
systems [6].
Several derivatized polypyrroles with solubilizing groups
have been synthesized and reported previously [2,7]. For exam-
ple, polypyrrole derivatives containing long alkyl or alkoxy
chain substituents were found to be soluble in several com-
∗ Corresponding author. Tel.: +61 2 42213127; fax: +61 2 42213114.
E-mail address: gwallace@uow.edu.au (G.G. Wallace).
(THF) [8]. The higher solubility in these polymers is achieved
by steric interference from the substituents, reducing interchain
interactions whilst also reducing the degree of orbital overlap
and the conductivity [2]. In addition, solutions of these deriva-
tized polypyrroles were unstable over time and precipitation of
the polymer occurred preventing further processing [2].
Recently, high molecular weight and soluble doped polypyr-
role containing no substituent on the pyrrole ring has been
synthesized [6]. The incorporation of di-(2-ethylhexyl) sulfosuc-
cinate (DEHS) dopant anion renders the polymer soluble in polar
and also weakly polar or non-polar solvents such as n-methyl
pyrrolidine (NMP), dimethyl sulfoxide (DMSO), dimethyl for-
mamide (DMF) and m-cresol [6]. The interaction of the DEHS
dopant with doped PPy chains is illustrated in Scheme 1. Free-
standing films exhibited conductivities in the range 10−3 to
3 S/cm depending on the solvent from which the films were
cast. Films cast from NMP could be stretched to 2.5 times their
original length to give a conductivity of close to 60 S/cm [6].
To the best of our knowledge there have been no previous
reports of wet-spinning soluble PPy to form continuous fibres.
One report has described the production of continuous PPy fibres
using an electrochemical cell where polymerization was initiated
at the tip of a needle, which was then slowly withdrawn from
the electrolyte to produce fibre [9]. However, production rates

0379-6779/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2007.12.008
 J. Foroughi et al. / Synthetic Metals 158 (2008) 104–107
Scheme 1. Schematic of interaction between Na+ DEHS− and oxidised polypyr-
role.
using this method were very slow. PPy has also been coated on
commercial yarn [10–12] with conductivities of ∼10−2 S/cm.
In this work the production of PPy fibres using a conventional
wet spinning approach has been demonstrated. Although the
method is not yet optimized, the produced fibres show quite
useful electronic, electrochemical and mechanical properties.
2. Experimental
2.1. Materials
Di-(2-ethylhexyl) sulfosuccinate sodium salt (Na+ DEHS− ),
ammonium peroxydisulfate (APS), dichloroacetic acid (DCAA,
98%), dimethyl propylene urea (DMPU) and dimethylfor-
mamide (DMF) were supplied by Sigma Aldrich and used as
received. Pyrrole monomer (95%, Aldrich) was used after dis-
tillation.
2.2. Preparation of spinning solution
Polypyrrole [(Py3 )+ (DEHS)− ]x powder was synthesized as
described previously [6]. The resultant powder after grinding
was filtered through a mesh of size 140 ␮m. 1.2 g of refined
[(Py3 )+ (DEHS)− ]x was slowly added to 10 g DCAA over a
period of 1 h with vigorously stirring. The spinning solution
was stirred another 2 h (200 rpm) at 0 ◦ C. Finally, a further 1 h
stirring under a dynamic vacuum ensured a bubble free solution
ready for fibre spinning.
Prior to spinning, the solution was passed through a 200 ␮m
filter using a nitrogen (N2 ) pressure vessel. The filtered solu-
tion was transferred to a syringe and syringe pump was used to
drive the spinning solution through a single hole spinneret with
a diameter of 150 ␮m and in to the coagulation bath at 100 ml/h.
The bath contained 40% (w/w) DMF in water at 20 ◦ C. The
fibre was held in the coagulation bath for 30 min, where the
fibre solidified. The fibre was then kept for 4 h in a water bath
to further reduce the solvent content, and then for 24 h in air at
room temperature prior to characterization.
105
2.3. Instrumentation
For electron microscopy fibre samples were cut after cooling
in liquid N2 to obtain circular undamaged cross-sections. Small
pieces of fibre were fixed vertically on an aluminum stub using
conductive glue. A sputter coater (Dynavac) was used for coat-
ing of a thin layer of gold on the cross-section and side wall of
the fibres (35 mA for 12 s under 200 mbar Ar). A Leica Stere-
oscan 440 scanning electron microscope (SEM) was used for
morphological studies of the fibres.
Tensile testing was carried out using a TA instrument dynamic
mechanical analyser. For tensile testing, a 10 mm gauge length
of fibre was stretched at a strain rate of 500 ␮m/min until the
sample broke or yielded at 25 ◦ C.
The electrical conductivity of the fibres was measured using
an in-house built four-point probe. The electrodes consisted
of four parallel rods at a spacing of 0.33 cm; the fibres were
connected to the parallel rods using silver paint (obtained
from SPI). A constant current was applied between two outer
electrodes using a potentiostat/galvanostat (Princeton Applied
Research Model 363). The potential difference between the inner
electrodes was measured using a digital multimeter 34401A
(Agilent).
The dynamic solvation diameter of PPy dispersions was mea-
sured using dynamic light scattering (ZS, Malvern, UK). A red
laser beam of 632 nm (He/Ne) was used. This system uses the
NIBS (non-invasive back scatter) technology where the back
scatter at 173◦ is detected. The use of NIBS technology reduces
multiple scattering effects since scattered light does not have to
travel through the entire sample, so that the size distribution at
higher concentrations of sample can be measured.
Ultra violet–visible–near infrared spectra were obtained
using a Cary 5000 spectrophotometer.
A three electrode electrochemical cylindrical cell
(15 mm × 50 mm) coupled to a Bioanalytical Systems
(Model CV27) potentiostat was used for cyclic voltammetry.
A 10 mm fibre was used as the working electrode with an
Ag/AgCl reference electrode and a Pt mesh counter electrode.
3. Results and discussion
The UV-vis/NIR spectra of PPy in selected solvents were
measured in the range from 300 to 2100 nm (Fig. 1). The
Fig. 1. UV–vis/NIR spectra of dilute solution (0.01%, w/w) of PPy in solvents
as labeled.
106 J. Foroughi et al. / Synthetic Metals 158 (2008) 104–107

Fig. 2. The size distribution obtained by light scattering of dilute solution

(0.01%, w/w) of PPy in solvents as labeled.

dichloroacetic acid (DCAA) solution shows higher absorption

intensity in the ∼300–2100 nm range than those of PPy solutions
in other solvents at the same nominal concentration. This higher
absorbance may be due to a better solubility of the polymer
or a different conformation (e.g. extended coil) of the polymer
chains. These results suggest that DCAA is the preferred solvent
for preparing high quality wet-spun PPy fibres. Light scattering
results (Fig. 2) show that an effective dispersion of the PPy was Fig. 3. Schematic diagram of spinning apparatus and photograph of a PPy fibre.
obtained in DMF, whilst PPy in both DMPU and DCAA was
present as a colloidal suspension with particle sizes <100 nm. Up the fibres were uniform, dense and non-porous. The surface
to 10 wt.% PPy could be suspended in DCAA, whereas 6 wt.% morphology was slightly rough but again, pore free.
and 8 wt.% could be suspended in DMF and DMPU, respec- Fig. 5 shows the stress-strain curves obtained from tensile
tively. DCAA was chosen for fibre spinning because it appeared testing of PPy fibre spun from DCAA. Analysis of these curves
to give a relatively more viscous and homogenous dispersion of indicates a stress at break in the range 20–25 MPa at ∼2% strain.
PPy. Young’s modulus of PPy fibre was measured to be ∼1.5 GPa.
Fibres were successfully spun from DCAA solution into long These mechanical properties are lower than previously reported
lengths as shown in Fig. 3. SEM micrographs of the PPy fibre for wet spun and drawn polyaniline (PAni) fibre [13], with a
are given in Fig. 4. As can be seen from the SEM cross-sections, breaking stress of 170 MPa and 3 GPa Young’s modulus. High

Fig. 4. SEM micrographs of PPy fibre at low (a and c) and higher (b and d) magnification showing the fibre cross-section (a and b) and surface (c and d).
 J. Foroughi et al. / Synthetic Metals 158 (2008) 104–107
Fig. 5. Stress–strain curves obtained from tensile testing of two PPy fibres.
Fig. 6. Cyclic voltammogram of PPy fibre. Potential was scanned between
−0.9 V and +0.4 V (vs. Ag/AgCl) in 1 M NaNO3(aq) at 100 mV/s.
molecular weight PAni was used in the previous work and it is
anticipated that further improvements to the PPy fibre mechan-
ical properties can be achieved by optimizing the synthesis
conditions to also increase the molecular weight.
Electrical conductivity and electroactivity of PPy fibres was
also determined. The average electrical conductivity of PPy
fibres was measured to be ∼3 S/cm. The conductivity is similar
to that previously obtained for PPy films cast with this dopant [6]
from DMF or DMSO solution. As reported in this earlier work,
higher conductivities may be possible by drawing of the PPy to
achieve molecular orientation. Further optimization of the fibre
spinning process may allow for fibre drawing, as demonstrated
previously for wet-spun polyaniline [13]. Cyclic voltammetry
for the PPy fibre in 1 M NaNO3 is shown in Fig. 6. Reason-
able electroactivity is observed in the PPy fibres as evidenced
by oxidation and reduction peaks at −0.3 and −0.5 V (Ag/AgCl
reference), respectively. The redox activity in these PPy fibres
occurs at lower potentials than previously reported for electro-
107
chemically prepared films (−0.3 to +0.1 V vs. Ag/AgCl for the
reduction potential [14]). The differences in redox potentials
probably reflect the influence of the dopant as well as possible
differences in molecular weight, cross-linking and molecular
order. The electroactivity observed in these fibres suggests that
the fibres may be useful for sensors, actuators and batteries as
previously shown for polyaniline fibres [5,7,13,15,16].
4. Conclusions
Continuous polypyrrole fibres have been produced for the
first time using a wet-spinning process. The process was enabled
by the formation of highly soluble non-functionalised PPy using
DEHS dopant as originally reported by Oh et al. [6]. Although
the synthesis conditions and spinning processes are not yet opti-
mized, fibres have been produced with reasonable mechanical,
electrical and electrochemical properties. Further improvements
in these properties are expected through the increase in PPy
molecular weight, drawing of the fibres and by incorporation of
carbon nanotubes as a high conductivity-reinforcing phase.
Acknowledgement
The authors gratefully acknowledge the financial support of
the Australian Research Council.
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