Synthetic Metals 243 (2018) 58–66

Contents lists available at ScienceDirect

Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Synthesis and characterization of a conductive and self-healing composite T

⁎
Marcela Mantese Sander , Carlos Arthur Ferreira
LAPOL –PPGE3M – Universidade Federal do Rio Grande do Sul (UFRGS), Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: An electrically conductive composite of poly(glycerol sebacate) (PGS) and polypyrrole (PPy) was prepared by
PGS solvent free synthesis. The PGS matrix was obtained with a 1:1 proportion of sebacic acid and glycerol. The PPy
PPy was prepared by chemical synthesis, using iron chloride as oxidant. Films containing 1, 3 and 5% PPy were
Electrical conductivity prepared by adding the conductive polymer, as a finely dispersed powder, into the PGS pre-polymer matrix. PGS
Self-healing
polymerization was confirmed by GPC, ATR-FTIR and NMR. Preparation time of the crosslinked film was de-
creased by 50% via the addition of PPy. The films were characterized by thermal and dynamic mechanical
analysis, indicating a thermally stable composite. The matrix behaved as an elastomer at room temperature. The
electrical conductivity of the composite films was in the order of 5 × 10−5 S/cm. Based on the chemical
characteristics of the matrix, the self-healing properties of PGS and its composites with PPy were investigated.
The results showed that the films can fully recover their mechanical strength after being cut and repaired at
130 °C for 24 h, retaining the electrical conductivity.

1. Introduction Liang et al [14], presented improved mechanical properties, like

Materials which possess several useful characteristics have proven
to be the most promising path in the development of lighter, more
sensitive and functional devices. So called “smart materials” are being
studied because they have multiple properties, are sensitive to external
stimuli and can be tailored as needed. Conductive polymer composites
(CPCs) are a type of smart material which combines the mechanical
properties of a host polymer matrix, with the electrical properties of a
conductive filler [1]. CPCs have been studied for many applications,
such as biomaterials [2,3], biosensors [4,5], gas sensors [6], as anti-
static covers for electronic devices [7], self-heating materials [8] and
coatings [9]. Most recently, Larimi et al [10] described a low-cost ultra-
stretchable CPC made into a commercial rubber-like adhesive patch.
This piezo-resistive strain sensor demonstrated great potential for
monitoring bio-signals and human motion. CPCs could be also obtained
in special forms, as demonstrated by Shu Ying et al [11], that obtained
an elastic conducting polypyrrole nanotube aerogel.
Both matrix and conductive filler can bestow special characteristics
to the CPC. They could be obtained from renewable feedstock, for ex-
ample, or enhance biodegradability and biocompatibility. Poly (gly-
cerol sebacate) (PGS) is a non-expansive biodegradable polyester pre-
pared by polycondensation of sebacic acid and glycerol, both obtained
from castor oil [12]. PGS alone has poor mechanical properties [13] but
using this polymer as a matrix in composites expands its range of useful
application. For example, a composite of PGS and Bioglass, proposed by
Young’s modulus and tensile strength, without compromised ex-
tensibility.
In this paper, we describe a new CPC, prepared by using a PGS
matrix and a polypyrrole (PPy) functionalisation component. PPy is an
electrically conductive and biocompatible polymer [15], even in small
amounts [16,17], used in several CPCs [18–20]. However, it is not fu-
sible and has poor solubility [21]. The combination of the rubber-like
characteristics of PGS and the electrically conductive properties of PPy,
makes this composite a potentially very interesting CPC. The physico-
chemical characteristics, thermal and conductive behaviour and mor-
phological aspects of the composite were studied. Additionally, based
on the chemical characteristics of PGS, it was hypothesized that this
polymer can exhibit self-healing properties [22]. Self-healing materials
are able to recover themselves after mechanical damage. Therefore, the
PGS as well as the composite polymer were tested for its self-healing
capability by evaluating their properties against some criteria, sug-
gesting a new method to identify potential intrinsic self-healing poly-
mers.
2. Experimental
2.1. Materials
Glycerol (Neon, purity 99.7%) and sebacic acid (Sigma-Aldrich,
purity 99%) were used as received. Pyrrole (Sigma-Aldrich, purity 98%)

⁎
Corresponding author at: Bento Gonçalves Av, 9500, Building 43426, PO Box 15010 Zip Code: 91501-970, Porto Alegre, Brasil.
E-mail address: marcela.sander@ufrgs.br (M.M. Sander).

https://doi.org/10.1016/j.synthmet.2018.06.003
Received 28 March 2018; Received in revised form 21 May 2018; Accepted 5 June 2018
0379-6779/ © 2018 Elsevier B.V. All rights reserved.
M.M. Sander, C.A. Ferreira
was distilled and stored under refrigeration prior to use. Ferric chloride
(Sigma-Aldrich, purity 99,9%) was used without further purification.
2.2. Synthesis of polymers
An equimolar mixture of glycerol and sebacic acid was reacted for
24 h at 130 °C, in a three-neck flask with a magnetic stirrer, under ni-
trogen flux in the first 5 h, to form the PGS prepolymer (a low molecular
weight polymer). The PGS film used as control was obtained by similar
synthesis, but the prepolymer was reacted for 48 h, and vacuum was
fitted in the last 4 h of reaction.
The PPy was synthetized at 0 °C in a jacketed vessel. An aqueous
solution of 0.06 mol of pyrrole and 0.11 mol of ferric chloride was
stirred for 6 h. The polymer was washed with water until it reached pH
6, filtered and dried in an oven for 24 h [23].
2.3. PGS/PPy film preparation
The films were prepared by adding the finely dispersed PPy powder
to the PGS prepolymer, at 130 °C, and stirring for 2 h. At this tem-
perature, the PGS prepolymer is a viscous liquid and the mixture
viscosity increased with successive PPy addition. The amount of PPy
added was 1, 3 and 5% w/w. The polymer mixtures, and PGS control,
were cast in silicon molds and the films were obtained by thermal-
curing, in a vacuum oven at 130 °C for 48 h.
3. Characterization
3.1. PGS synthesis
PGS synthesis was confirmed by gel permeation chromatography
(GPC) and NMR (nuclear magnetic resonance) of the prepolymer. For
GPC analysis a 1 wt% PGS prepolymer solution was prepared in tetra-
hydrofuran (THF). The elution rate of the mobile phase (also THF) was
adjusted to 1 mL/min, and 1 μL of solution was injected in a chroma-
tograph (Viscotek model VE2001) with a Viscotek TDA 302 detector.
The proton NMR spectra was obtained in a Varian 400 MHz. The sample
was prepared with 50 mg of prepolymer in 5 mL of deuterated chloro-
form (CDCl3) with trimethylsilane (TMS).
3.2. Composite characterization
The crosslinked polymer and composites were characterized for
chemical bonds with attenuated total reflectance Fourier transform
infrared spectroscopy (ATR-FTIR). Spectral images were acquired in
ATR mode using a Perkin-Elmer Frontier. Data were collected in 64
scans in the wavenumber range between 400-4000 cm−1 and spectral
resolution of 4 cm−1.
Scanning electron microscopy (SEM) of cryogenically fractured
cross-sections was performed on a scanning electron microscope
(Phenom World, model Pro X (Phenom, Netherlands)). The samples
were sputtered with gold in a Balzers model Sputter Coater SCD 050, for
100 s, under vacuum and at a deposition current of 40 mA.
The thermal properties of the films were evaluated with a differ-
ential scanning calorimeter (DSC) (TA instrument, model Q20), using
heating/cooling rates of 10 °C/min and 50 mL/min nitrogen flow. The
samples weighed approximately 6 mg.
The thermal stability of the films was measured using a thermo-
gravimetric analyzer (TGA) (TA Instruments, model TGA-50). The
temperature was increased from 30 °C to 800 °C at a rate of 20 °C/min,
under nitrogen flow of 90 mL/min.
The electrical conductivity of the PGS/PPy films was measured at
room temperature using the four-point probe technique (Cascade
Microtech model CS 4–64). A current source (Keithley model 2040) was
used for the supply of constant current through the two outer probes,
and the current was measured in the inner probes. The films were cut in
59
Synthetic Metals 243 (2018) 58–66
1 cm² squares. Using the values of current, voltage and thicknesses of
the films, the resistivity was calculated using the following formula.
ρ = (V/I) t (1)
where ρ = electrical resistivity, V = voltage, I = current and
t = thickness (cm). The electrical conductivity (σ) was then calculated
using the following equation:
σ = 1/ρ (2)
Tensile tests were performed in an Instron model Emic 23-5D,
equipped with a 50 N cell load, at room temperature, at a rate of
50 mm/min. The specimens (n = 4) were cut in a dog bone shape, with
dimensions 35 × 2 x t mm (total length x width in the neck section x
film thickness, measured individually). The ultimate tensile strength
(UTS) and elongation at break were measured at the highest stress that
the material could reach. Blue Hill 3 software was used for data ana-
lysis.
3.3. Self-healing evaluation
As there are no standard methods to evaluate the self-healing
properties of polymers, it was decided to investigate the novel materials
both quantitatively and pure PGS qualitatively. Hence, UTS and elon-
gation at break data from tensile tests and photographs of self-healed
and undamaged samples were compared.
For the quantitative tests, specimens cut in a dog bone shape were
tested as described above, in tensile test. Samples were cut in half with
a blade and put together by closely fitting the two halves again after
30 s. The specimens were kept at four temperatures, 25, 37, 60 and
130 °C, for 2 and 24 h. Three samples for each condition were prepared.
For the qualitative evaluation specimens of pure PGS with dimen-
sions of 8 × 30 x 5 mm (width, length and thickness, respectively) were
kept at 25 and 130 °C, for 2 and 24 h. Each was photographed while
being manually stretched in axial direction, with tweezers. Differently
for the quantitative test, and in order to best visualize the healed in-
terface, one half of pure PGS specimen was colored with 1 drop of green
pigment (Food Green 3) before thermal curing.
4. Results and discussion
4.1. Polymer synthesis
The PGS prepolymer was successfully prepared by equimolar poly-
condensation of glycerol and sebacic acid. A schematic diagram of the
fabrication process of PGS control and PGS/PPy composites is shown in
Fig. 1. The partly cross-linked PGS prepolymer had an average mole-
cular weight (Mw) of 15,900 and a number average molecular weight
(Mn) of 2,603, with a polydispersity index (PDI) of 6.1, as measured by
GPC. These results are similar to those previously reported [24]. The
FTIR spectra of the PGS control, after being cured, (and the composite
with PPy) can be seen in Fig. 2.
Characteristic spectra were obtained for PGS, showing the ester
bond formation. The main peaks are located at 3400 cm−1 (OeH
stretching), two peaks at 2926 and 2853 cm−1 (alkane groups) and
1734 cm−1 (C]O stretching). In the proton NMR spectra of the PGS
prepolymer (Fig. 3) the peaks at 1.31, 1.62, and 2.35 ppm were as-
signed to the methylene protons of sebacic acid; peaks from 4.05 to
4.35 ppm and 5.05–5.30 ppm were observed due to protons in the
glycerol [25]. The composition ratio of glycerol to sebacate (0.93:1) in
the PGS prepolymer was estimated by the integral area ratio of de-
scribed peaks. This slight decrease in glycerol amount, when compared
to initial 1:1 M ratio, was described in previous studies [26] and is at-
tributed to unreacted glycerol molecules evaporating and being carried
away by nitrogen flux in the first 5 h of reaction.
M.M. Sander, C.A. Ferreira Synthetic Metals 243 (2018) 58–66

Fig. 1. Schematic diagram of the fabrication process of PGS control and PGS/PPy composites.

4.2. Composite preparation PPy in the crystallizable matrix and, consequently, favoring the con-
ductivity of the composite. The bound rubber theory states that the
The elastomeric composite films were successfully prepared by the adsorption of macromolecules on a filler surface proceeds by bond
proposed route. Addition of PPy resulted in decreased prepolymer formation [29].
preparation time, from 48 h to 24 h, when compared to the PGS control
film. Furthermore, the film fabrication method developed in this work
4.3. Microstructural evaluation (SEM images)
is a solvent-free process, and therefore more environmentally friendly
than previously described methods [24,27]. When comparing the ATR-
SEM images for PGS and the composites are shown in Fig. 5. The
FTIR spectra of the PGS control and the PGS/PPy composite (Fig. 2), the
grey regions represent the PGS matrix and the spherical shapes (in-
peaks associated to the PPy can be identified at 1560 and 880 cm−1.
dicated by red arrows) are dispersed PPy polymer particles. Before
These are attributed to the bending and stretching of the amine groups,
sputtering the samples with gold, the composition of each phase was
respectively. A slight decrease in hydroxyl groups peak in the PGS/PPy
characterized by EDS, confirming that the spheres contained nitrogen,
composite spectra, and appearance of a peak associate to amine bond,
indicating that is formed by PPy.
can also be seen in Fig. 4, indicating the formation of hydrogen bonds
The surface of composites is rough, while the PGS control matrix is
between the polymers chains [25]. Corres et al [28] cited this hydrogen
smooth, indicating that the PPy is well dispersed, with some con-
bonding interactions as playing a considerable role on the morphology
centrations. In the composites with lower PPy content (1 and 3%), the
of the polymer matrix, providing a more homogeneous distribution of
PGS matrix seems to cover almost all of the conductive polymer,

Fig. 2. ATR-FTIR spectra for the PGS control film (a) and the PGS/PPy composite film (b). The main peaks are assigned.

60
M.M. Sander, C.A. Ferreira
Fig. 3. PGS molecule and NMR spectra from the PGS prepolymer. The peaks are associated to the molecule by corresponding letters.
Fig. 4. PGS and PGS/PPy 5% ATR-FTIR spectra detail. The arrows indicate the
decrease in hydroxyl group transmittance peak and appearance of amine group
transmittance peak in the spectra composite.
composing a continuous layer with few spheres in the surface of the
fracture cross-section, not affecting the conducting network formed.
However, for the 5% composite, the quantity of PPy on the surface is
larger, showing that the matrix was no longer able to cover all the
conductive polymer spheres, reached a wettability limit. This phe-
nomenon seems to affect the thermal and electrical conductivity be-
havior of the composite, as described in next sections.
4.4. Thermal characteristics
The PGS polymer and its composites are thermally stable up to
around 400 °C, as demonstrated by TGA. Polymer decomposition is a
single event, starting at 420 °C. The addition of PPy, an amorphous
polymer [30], does not affect the thermal stability, but slows down the
degradation profile, as displayed in Fig. 6a.
PGS is a thermoset elastomer, formed by the crosslinking of
61
Synthetic Metals 243 (2018) 58–66
prepolymers and presents two different phases: gel and sol [31]. The gel
phase is formed by the crosslinked network which is not soluble in
organic solvents like THF. The sol phase, on the other hand, is soluble.
It is formed by non-crosslinked chains and acts as a plasticizer for the
gel phase. Fig. 6b shows the melting and crystallization DSC curves, and
Table 1 lists the melting temperature (Tm), crystallization temperature
(Tc), glass transition temperature (Tg) and absolute melt enthalpy (ΔH)
of the films. The PGS and PGS/PPy composites present melting and
crystallization peaks, relative to a sol phase. The gel phases give a
crosslinked 3D structure to the elastomer, resulting in a solid and
stretchable polymer at room temperature. The addition of PPy increases
the melting temperature and decreases the crystallization temperature
and melting enthalpy of the composite (with the exception of the
composite with 5% PPy). The amorphous polymer interacts with the sol
phase mostly by hydrogen bonds, as shown in ATR-FTIR spectra. It is
hindering the movement of molecular chain segments and, conse-
quently, reducing Tg [32].
Taking into account the wettability limit of the PGS matrix, a sa-
turation plateau was reached with 3% of PPy [33]. In further additions,
the phases compatibility decreased, as could been seeing by the thermal
characteristics and SEM images of PGS/PPy 5% composites.
4.5. Electrical conductivity of composites
The pure PPy polymer had an electrical conductivity of 4.6 × 102 S/
cm. Conductivity of around 10−5 S/cm was measured for all the PGS/
PPy composites, with the highest value measured for 3% of PPy, as
summarized in Table 2. As explained in section 4.4, the wettability limit
was reached with 3% of PPy in the matrix. Further additions do not
increase the conductivity and also seems to disturb the percolation
threshold by forming segregated structures [34].
The results indicate that the composite is a semiconducting mate-
rial. Other authors have reported similar conductivity results for com-
posites comprising a PGS matrix and another conductive polymer, such
as polyaniline (PGS/PANI) [35], but in this instance more than 15%
PANI was used. As pointed by Merlini et al [36] in a study about a CPC
made with PVDF and PPy, a good compatibility between the polymers
M.M. Sander, C.A. Ferreira Synthetic Metals 243 (2018) 58–66

Fig. 5. SEM images of cryogenically fractured cross-sections of PGS and its composites with 1, 3 and 5% of PPy.

makes the CPC a semiconductor even with low contents of PPy, that
induces a conducting network formation into the matrix. Promising
potential for application as cardiac repair patch material, for example,
is clear from a comparison with the electrical conductivity of myo-
cardial tissue (1.6 × 10−3 S/cm (longitudinally) and 5 × 10-5 S/cm
(transversally)) [37].
4.6. Self-healing evaluation
As there are no standard methods to characterize the self-healing
abilities of polymers, we introduce a simple method for evaluation.
Gyarmati et al. [38] suggested some criteria to classify self-healing
hydrogels. We adapted these criteria for polymers in general, with the
goal to expand the scope. The criteria can be used to assess if a material

Fig. 6. TGA and DSC curves for PGS and PGS/PPy composites.

62
M.M. Sander, C.A. Ferreira Synthetic Metals 243 (2018) 58–66

Table 1 Table 3
Tm, Tc, melt enthalpy and Tg for PGS control and PGS/PPy composites. Results of recovered elongation at break and recovered UTS from quantitative
self-healing tests.
Sample Tm (°C) Tc (°C) ΔHf (J/g) Tg (°C)
Sample Recovered elongation (%) Recovered UTS (%)
PGS Control 1,83 −17,7 28,6 −26,1
PGS/PPy 1% 2,61 −17,9 27,1 −26,2 PGS Control
PGS/PPy 3% 3,30 −18,6 21,9 −26,3 2 h 25 °C 22,0 10,00
PGS/PPy 5% 1,96 −18,7 23,6 −26,8 24 h 25 °C 21,6 15,00
2 h 37 °C 16,3 15,00
24 h 37 °C 14,4 15,00
Table 2 2 h 60 °C 17,7 20,00
24 h 60 °C 19,3 20,00
Electrical conductivity for PGS/PPy composites.
2 h 130 °C 61,4 15,00
Sample S (S/cm) 24 h 130 °C 25,2 100,00

PGS/PPy 1%
PGS/PPy 1% 1.83 × 10−5
2 h 25 °C 64,5 9,52
PGS/PPy 3% 5.10 × 10−5
24 h 25 °C 70,1 9,52
PGS/PPy 5% 1.96 × 10−5
2 h 37 °C 14,7 19,05
24 h 37 °C 13,0 19,05
2 h 60 °C 15,9 23,81
can be classified as an intrinsically self-healing polymer, namely, a 24 h 60 °C 19,8 23,81
polymer which possesses a chemical structure such that it is able to self- 2 h 130 °C 65,3 9,52
24 h 130 °C 19,7 128,57
repair damage [39]. Accordingly, candidates which are classified as
self-healing must meet the following criteria: PGS/PPy 5%
a) Presence of specific functional groups such as reversible bonds, 2 h 25 °C 30,2 25,00
24 h 25 °C 21,9 15,63
side groups which can form non-covalent bonds and networks, side 2 h 37 °C 10,8 21,9
ionomers pairs, etc., verified successfully by spectroscopic or equivalent 24 h 37 °C 11,0 21,9
methods; 2 h 60 °C 7,3 15,6
b) Macroscopic self-healing tests, using imaging methods; 24 h 60 °C 5,6 9,4
2 h 130 °C 74,0 21,88
c) Healing efficiency assessed by measuring mechanical properties.
24 h 130 °C 16,2 75,00
The results could be presented as “% of property recovered” relative to
undamaged specimens. The dynamics, temperature and time depen-
dence of the self-healing process should be studied. it is possible that the curing process of PGS was not complete before the
Taking into account that the esterification reaction is reversible and self-healing analysis was carried out. This could explain how the
that the PGS presents some hydroxyl groups attached to the chain, crosslinked network increased and made the matrix stronger, evidenced
which are able to make hydrogen bonds, we hypothesized that the PGS in the increased UTS result.
could repair itself after being damaged. To investigate the self-healing The electrical conductivity of the composites was tested in healed
capability, we tested specimens of pure PGS and its composites with specimens, after conditioned for 24 h at 25, 37, 60 and 130 °C. The
PPy (1 and 5%) which were healed after being damaged and subjected measured values were compared with the original electrical con-
to different conditions of temperature and contact time. The values for ductivity test showed at section 4.5. The results are presented in the
comparative recovered elongation at break and UTS are presented in Fig. 9. The electrical conductivity decreases as the healing temperature
Table 3. Fig. 7 shows a bar chart comparing results for elongation at increases. However, there is no significant change in the conductivity
break and UTS. magnitude, keeping it above 10−5 S/cm. Therefore, even after healed,
First, we analyzed the results for pure PGS. The polymer specimens the composites remain semiconductor CPCs.
healed at 25, 37 and 60 °C recovered around 20% of elongation at break
and up to 20% of UTS, for both contact times (2 and 24 h) when
compared to original PGS results obtained in standard tensile tests. At 5. Conclusion
130 °C, two distinguishing behaviors were detected. With 2 h contact,
the specimens recovered better elongation at break than the specimens A novel conductive polymer composite, prepared with PGS and PPy,
put in contact for 24 h. On the other hand, the percentage of recovered was obtained successfully via a solvent free route. Prepolymer pre-
UTS increased with contact time, reaching 100% at 24 h of contact. The paration time for the composite was decreased by 50% compared to the
photographs shown in Fig. 8 illustrate this behavior. These significant PGS control film. At room temperature, the composites were black,
results validate the classification of PGS as an intrinsically self-healing rubbery and had electrical conductivity of around 10−5 S/cm. CPC
polymer when kept at high temperature. It can repair itself by re- thermal and electrical properties are influenced by the amount of
covering 100% of the maximum stress that the original polymer can conductive filler added to the polymer matrix. The best compatibility
resist while being stretched before breaking. The ability to self-repair is between matrix and filler was reached with 3% of PPy.
firstly attributed to the reversibility of the ester bonds and the hydroxyl We described the self-healing characteristic of PGS, which can be
groups attached to main backbone which are able to form inter- classified as an intrinsic self-healing polymer. After 24 h of contact at
molecular hydrogen bonds. Furthermore, the PGS has a sol phase, 130 °C, the healed PGS sample restored 100% of maximum strain at
which ensures free volume and hence good mobility of end-chains to break, when compare with an undamaged sample. Similar behavior was
repair the broken bonds. High temperatures favored the diffusion chain observed for PGS/PPy composites, indicating that the self-healing
process and advanced self-healing. properties of PGS is retained in the composites. The electrical con-
The composites presented similar results, as can be seen in Table 3, ductivity remains above 10−5 S/cm, ensuring the composite as a
indicating that the filler does not affect significantly the self-healing semiconductor CPC after healed.
capability. For both PPy loading, the best results were achieved for the Overall, the combination of the unique properties of PPy and the
specimens healed at 130 °C, which recovered up to 74% of elongation at PGS makes the CPCs potentially suitable for the development of new
break with 2 h contact and reached more than 100% of UTS after 24 h devices, such as sensors, biomedical equipment, smart coatings and
contact. This result indicates a very good self-healing process. However, more.

63
M.M. Sander, C.A. Ferreira Synthetic Metals 243 (2018) 58–66

Fig. 7. Bar chart comparing results for (a) elongation at break and UTS for healed and undamaged specimens of PGS control and composites, in the quantitative tests.

Fig. 8. Photographs of PGS control self-healing qualitative tests.

64
M.M. Sander, C.A. Ferreira
Fig. 9. Electrical conductivity of composites, after healed for 24 h at 25, 37, 60 and 130 °C.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Authors would like to thank Brazilian Agencies CNPq, CAPES,
FINEP and FAPERGS by their financial support. The authors also
gratefully acknowledge to Dr. Mariska Hattenberger for the helpful
discussions.
References
[1] H. Pang, L. Xu, D. Yan, Z. Li, Progress in polymer science conductive polymer
composites with segregated structures, Prog. Polym. Sci. 39 (2014) 1908–1933,
http://dx.doi.org/10.1016/j.progpolymsci.2014.07.007.
[2] B. Guo, L. Glavas, A.-C. Albertsson, Biodegradable and electrically conducting
polymers for biomedical applications, Prog. Polym. Sci. 38 (2013) 1263–1286,
http://dx.doi.org/10.1016/j.progpolymsci.2013.06.003.
[3] E. Číková, M. Mičušík, A. Šišková, M. Procházka, P. Fedorko, M. Omastová,
Conducting electrospun polycaprolactone/polypyrrole fibers, Synth. Met. 235
(2018) 80–88, http://dx.doi.org/10.1016/j.synthmet.2017.11.011.
[4] A. Guiseppi-Elie, Electroconductive hydrogels: synthesis, characterization and
biomedical applications, Biomaterials. 31 (2010) 2701–2716, http://dx.doi.org/10.
1016/j.biomaterials.2009.12.052.
[5] E. Nazarzadeh Zare, M. Mansour Lakouraj, M. Mohseni, Biodegradable polypyrrole/
dextrin conductive nanocomposite: synthesis, characterization, antioxidant and
antibacterial activity, Synth. Met. 187 (2014) 9–16, http://dx.doi.org/10.1016/J.
SYNTHMET.2013.09.045.
[6] S. Erturan, B. Yalvaç, S. Toraman, Polymerization of pyrrole and thiophene on
polyethylene adipate electrodes, Turkish J. Chem. 22 (1998) 161–166.
[7] W. Zhai, S. Zhao, Y. Wang, G. Zheng, K. Dai, C. Liu, C. Shen, Segregated conductive
polymer composite with synergistically electrical and mechanical properties,
Compos. Part. A Appl. Sci. Manuf. 105 (2018) 68–77, http://dx.doi.org/10.1016/j.
compositesa.2017.11.008.
[8] P. Tang, R. Zhang, Z. Chen, B. Yang, Y. Bin, Effect of γ-ray irradiation on the mi-
crostructure and self-heating property of carbon fiber/polyethylene composite
films, Compos. Part. A Appl. Sci. Manuf. 78 (2015) 174–180, http://dx.doi.org/10.
1016/j.compositesa.2015.07.021.
[9] B.M. Bailey, Y. Leterrier, S.J. Garcia, S. Van Der Zwaag, V. Michaud, Electrically
conductive self-healing polymer composite coatings, Prog. Org. Coatings. 85 (2015)
189–198, http://dx.doi.org/10.1016/j.porgcoat.2015.04.013.
[10] S. Reza, H. Rezaei, M. Oyatsi, A.O. Brien, M. Hoorfar, H. Najjaran, Low-cost ultra-
stretchable strain sensors for monitoring human motion and bio-signals, Sensors
Actuators A. Phys. 271 (2018) 182–191, http://dx.doi.org/10.1016/j.sna.2018.01.
028.
[11] S. Ying, W. Zheng, B. Li, X. She, H. Huang, L. Li, Z. Huang, Y. Huang, Z. Liu, X. Yu,
Facile fabrication of elastic conducting polypyrrole nanotube aerogels, Synth. Met.
218 (2016) 50–55, http://dx.doi.org/10.1016/J.SYNTHMET.2016.05.002.
[12] R. Rai, M. Tallawi, A. Grigore, A.R. Boccaccini, Synthesis, properties and biome-
dical applications of poly(glycerol sebacate) (PGS): a review, Prog. Polym. Sci. 37
(2012) 1051–1078, http://dx.doi.org/10.1016/j.progpolymsci.2012.02.001.
[13] I.H. Jaafar, M.M. Ammar, S.S. Jedlicka, R.A. Pearson, J.P. Coulter, Spectroscopic
evaluation, thermal, and thermomechanical characterization of poly(glycerol-
65
Synthetic Metals 243 (2018) 58–66
sebacate) with variations in curing temperatures and durations, J. Mater. Sci. 45
(2010) 2525–2529, http://dx.doi.org/10.1007/s10853-010-4259-0.
[14] S. Liang, W.D. Cook, Q. Chen, Physical characterization of poly(glycerol sebacate)/
Bioglass composites, Polym. Int. 61 (2012) 17–22, http://dx.doi.org/10.1002/pi.
3165.
[15] J. Upadhyay, A. Kumar, B. Gogoi, A.K. Buragohain, Biocompatibility and anti-
oxidant activity of polypyrrole nanotubes, Synth. Met. 189 (2014) 119–125, http://
dx.doi.org/10.1016/j.synthmet.2014.01.004.
[16] S. Geetha, C.R.K. Rao, M. Vijayan, D.C. Trivedi, Biosensing and drug delivery by
polypyrrole, Anal. Chim. Acta. 568 (2006) 119–125, http://dx.doi.org/10.1016/j.
aca.2005.10.011.
[17] M. Mravčáková, M. Omastová, P. Pötschke, A. Pozsgay, B. Pukánszky, J. Pionteck,
Poly(propylene)/montmorillonite/polypyrrole composites: structure and con-
ductivity, Polym. Adv. Technol. 17 (2006) 715–726, http://dx.doi.org/10.1002/
pat.765.
[18] F. Liu, Y. Yuan, L. Li, S. Shang, X. Yu, Q. Zhang, S. Jiang, Y. Wu, Synthesis of
polypyrrole nanocomposites decorated with silver nanoparticles with electro-
catalysis and antibacterial property, Compos. Part. B Eng. 69 (2015) 232–236,
http://dx.doi.org/10.1016/J.COMPOSITESB.2014.09.030.
[19] J. Hur, K. Im, S.W. Kim, J. Kim, D.-Y. Chung, T.-H. Kim, K.H. Jo, J.H. Hahn, Z. Bao,
S. Hwang, N. Park, Polypyrrole/Agarose-based electronically conductive and re-
versibly restorable hydrogel, ACS Nano. 8 (2014) 10066–10076, http://dx.doi.org/
10.1021/nn502704g.
[20] H. Huang, J. Wu, X. Lin, L. Li, S. Shang, M.C. Yuen, G. Yan, Self-assembly of
polypyrrole/chitosan composite hydrogels, Carbohydr. Polym. 95 (2013) 72–76,
http://dx.doi.org/10.1016/J.CARBPOL.2013.02.071.
[21] E. Tavakkol, H. Tavanai, A. Abdolmaleki, M. Morshed, Production of conductive
electrospun polypyrrole/poly(vinyl pyrrolidone) nanofibers, Synth. Met. 231
(2017) 95–106, http://dx.doi.org/10.1016/J.SYNTHMET.2017.06.017.
[22] S.J. Garcia, Effect of polymer architecture on the intrinsic self-healing character of
polymers, Eur. Polym. J. 53 (2014) 118–125, http://dx.doi.org/10.1016/j.
eurpolymj.2014.01.026.
[23] M.A. Hocevar, Biossensores estruturados com polímeros condutores para detecção
de glicose, Universidade Federal do Rio Grande do Sul, 2016. https://sabi.ufrgs.br/
F/63ICGT88LKEE5KIQN5XF8AYRQ7AKNABDU32PLLPL4VMT9PU7BI-11256?
func=full-set-set&set_number=018566&set_entry=000003&format=999.
[24] M.J. Kim, M.Y. Hwang, J. Kim, D.J. Chung, Biodegradable and elastomeric poly
(glycerol sebacate) as a coating material for nitinol bare stent, Biomed. Res. Int.
2014 (2014), http://dx.doi.org/10.1155/2014/956952.
[25] Y. Wu, L. Wang, B. Guo, P.X. Ma, Injectable biodegradable hydrogels and microgels
based on methacrylated poly(ethylene glycol)-co-poly(glycerol sebacate) multi-
block copolymers: synthesis, characterization, and cell encapsulation, J. Mater.
Chem. B. 2 (2014) 3674–3685, http://dx.doi.org/10.1039/C3TB21716G.
[26] X. Li, A.T.L. Hong, N. Naskar, H.J. Chung, Criteria for quick and consistent synthesis
of poly(glycerol sebacate) for tailored mechanical properties, Biomacromolecules.
16 (2015) 1525–1533, http://dx.doi.org/10.1021/acs.biomac.5b00018.
[27] D. Dippold, M. Tallawi, S. Tansaz, J.A. Roether, A.R. Boccaccini, Novel electrospun
poly(glycerol sebacate)-zein fiber mats as candidate materials for cardiac tissue
engineering, Eur. Polym. J. 75 (2016) 504–513, http://dx.doi.org/10.1016/j.
eurpolymj.2015.12.030.
[28] M. Ángeles Corres, A. Mugica, P.M. Carrasco, M. Milagros Cortázar, Effect of
crystallization on morphology-conductivity relationship in polypyrrole/poly(e-ca-
prolactone) blends, Polym. (Guildf.). 47 (2006) 6759–6764, http://dx.doi.org/10.
1016/j.polymer.2006.07.042.
[29] B. Meissner, Theory of bound rubber, Rubber Chem. Technol. 48 (1975) 810–818,
http://dx.doi.org/10.5254/1.3539688.
[30] F. Ghamouss, A. Brugère, A.C. Anbalagan, B. Schmaltz, E. Luais, F. Tran-Van, Novel
glycerol assisted synthesis of polypyrrole nanospheres and its electrochemical
M.M. Sander, C.A. Ferreira
properties, Synth. Met. 168 (2013) 9–15, http://dx.doi.org/10.1016/j.synthmet.
2013.02.005.
[31] Q. Liu, M. Tian, R. Shi, L. Zhang, D. Chen, W. Tian, Structure and properties of
thermoplastic poly(glycerol sebacate) elastomers originating from prepolymers
with different molecular weights, J. Appl. Polym. Sci. 104 (2007) 1131–1137,
http://dx.doi.org/10.1002/app.25606.
[32] Q. Liu, J. Wu, T. Tan, L. Zhang, D. Chen, W. Tian, Preparation, properties and
cytotoxicity evaluation of a biodegradable polyester elastomer composite, Polym.
Degrad. Stab. 94 (2009) 1427–1435, http://dx.doi.org/10.1016/j.
polymdegradstab.2009.05.023.
[33] H. Pang, L. Xu, D.X. Yan, Z.M. Li, Conductive polymer composites with segregated
structures, Prog. Polym. Sci. 39 (2014) 1908–1933, http://dx.doi.org/10.1016/j.
progpolymsci.2014.07.007.
[34] H. Deng, L. Lin, M. Ji, S. Zhang, M. Yang, Q. Fu, Progress on the morphological
control of conductive network in conductive polymer composites and the use as
electroactive multifunctional materials, Prog. Polym. Sci. 39 (2014) 627–655,
http://dx.doi.org/10.1016/j.progpolymsci.2013.07.007.
[35] T.H. Qazi, R. Rai, D. Dippold, J.E. Roether, D.W. Schubert, E. Rosellini, N. Barbani,
66
Synthetic Metals 243 (2018) 58–66
A.R. Boccaccini, Development and characterization of novel electrically conductive
PANI-PGS composites for cardiac tissue engineering applications, Acta Biomater. 10
(2014) 2434–2445, http://dx.doi.org/10.1016/j.actbio.2014.02.023.
[36] C. Merlini, G.M.D.O. Barra, T.M. Araujo, A. Pegoretti, The effect of compressive
stress on the electrically resistivity of poly(vinylidene fluoride)/polypyrrole blends,
Synth. Met. 196 (2014) 186–192, http://dx.doi.org/10.1016/j.synthmet.2014.08.
002.
[37] K.C. Roberts-Thomson, P.M. Kistler, P. Sanders, J.B. Morton, H.M. Haqqani,
I. Stevenson, J.K. Vohra, P.B. Sparks, J.M. Kalman, Fractionated atrial electrograms
during sinus rhythm: relationship to age, voltage, and conduction velocity, Hear.
Rhythm. 6 (2009) 587–591, http://dx.doi.org/10.1016/j.hrthm.2009.02.023.
[38] B. Gyarmati, B.Á. Szilágyi, A. Szilágyi, Reversible interactions in self-healing and
shape memory hydrogels, Eur. Polym. J. 93 (2017) 642–669, http://dx.doi.org/10.
1016/j.eurpolymj.2017.05.020.
[39] K. Urdl, A. Kandelbauer, W. Kern, U. Müller, M. Thebault, E. Zikulnig-Rusch, Self-
healing of densely crosslinked thermoset polymers—a critical review, Prog. Org.
Coatings. 104 (2017) 232–249, http://dx.doi.org/10.1016/j.porgcoat.2016.11.010.