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REVIEW View Journal | View Issue
Electrically conductive polymers and composites
for biomedical applications
Cite this: RSC Adv., 2015, 5, 37553
Open Access Article. Published on 16 April 2015. Downloaded on 7/1/2025 11:26:52 PM.
Gagan Kaur,* Raju Adhikari, Peter Cass, Mark Bown and Pathiraja Gunatillake*
Electrically conductive polymeric materials have recently attracted considerable interest from academic
and industrial researchers to explore their potential in biomedical applications such as in biosensors,
drug delivery systems, biomedical implants and tissue engineering. Conventional conductive
homopolymers such as polypyrrole and PEDOT show promising conductivity for these applications,
however their mechanical properties, biocompatibility and processability are often poor. This has led to
more recent attention being directed towards conductive polymeric composites comprised of biostable/
biocompatible polymers with dispersed conductive fillers such as graphene, carbon nanotubes and
metallic nanoparticles. The major objective of this paper is to provide an up to date review of the recent
Received 30th January 2015
Accepted 15th April 2015
investigations conducted in the development of conductive polymer composites focussing on the
methods of their preparation, underlying concepts of their conductivity and the ways to tailor their
DOI: 10.1039/c5ra01851j
properties. Furthermore, recent progress made in conventional conducting polymers and their
www.rsc.org/advances composites/blends for biomedical applications is also discussed.
ionization potential and high electron affinities. These unique
1. Introduction properties make these materials suitable for applications as
Since the discovery of intrinsically conducting polymers, thin lm transistors, organic light emitting diodes, sensors,
researchers have explored their unusual electronic properties supercapacitors, organic solar cells and electrochromic
for a wide range of applications. Due to the presence of a displays. Many research groups have extensively investigated
conjugated p-electron backbone these polymers exhibit elec- conducting polymers for these applications and a number of
tronic properties such as low energy optical transmission, low excellent reviews are available.1–12
More recently, conducting polymers and electroactive
polymers have received the attention of researchers to explore
CSIRO Manufacturing Flagship, Bayview Avenue, Clayton, VIC 3168, Australia.
E-mail: [email protected]; [email protected] their potential in biomedical applications. This new generation
Gagan Kaur received her MSc Raju Adhikari completed his
Hons. (Chemistry) from Guru PhD in organic chemistry from
Nanak Dev University, India University of Delhi. He did his
(1997) and her PhD (Polymer post-doctoral studies at CSIRO
Chemistry) from Monash Molecular Science in 1992 and
University, Australia (2013). later at Universitat of Hohen-
Gagan is currently working as a heim, Germany and rejoined
Postdoctoral Fellow at CSIRO in 1995. He is one of the
Commonwealth Scientic and inventors of two platform tech-
Industrial Research Organisa- nologies Elast-Eon™ and
tion, Melbourne, Australia. NovoSorb™ which are a family
Gagan's research interests lie in of biostable and biodegradable
the synthesis and development polyurethanes. Beside biomate-
of novel polymeric materials for biomedical, nanoscience and rials, he has worked in OLED and Agriculture polymer areas and
industrial applications. Her research interests also lie in the contributed signicantly to technology and product development
electroactive biomaterials, living radical polymerizations and drug in both elds. He is currently working as a Principal Research
delivery. Scientist and holds an Adjunct A/Professor position at RMIT
University.
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of “smart” biomaterials have been investigated for applications
in biosensors; coatings on conventional electrodes used in
neural sensing and stimulation; electrically induced drug
release and delivery systems; modulators of activities of nerve,
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cardiac, skeletal muscle, and bone cells; and in emerging
technologies such as tissue engineering.13 The most widely
investigated conducting polymers for biomedical applications
include polypyrrole, polyaniline, polythiophene and its deriv-
atives such as poly(3,4-ethylenedioxythiophene).14–17 Fig. 1
presents an overview of a broad conductivity range of con-
ducting polymers and conductive polymeric composites.
Open Access Article. Published on 16 April 2015. Downloaded on 7/1/2025 11:26:52 PM.
Fig. 1Conductivity range of conducting polymers and conductive
Most studies have focused on investigating the interaction of polymeric composites.
these polymers with biological tissues using in vitro assays and
strategies to improve biocompatibility. Tailoring conducting
polymers to have appropriate mechanical properties, electrical composites. A brief introduction to the chemistry and proper-
conductivity, processability as well as acceptable biocompati- ties of the well known conducting polymers followed by review
bility has been the major challenge in application of this class of of the recent literature on conductive composites is provided.
polymers for clinically useful biomedical implants and devices.
Development of composites of conducting polymers with con-
ducting nanoparticles along with non-conducting polymers to 2. Conducting polymers
improve mechanical performance and biocompatibility has
The derivatives of polypyrrole with resistivities as low as 1 U cm
been one of the recent approaches in attempting to overcome
were rst reported in 1963 by Australian scientists Bolto and
some of these limitations. The major focus of this paper is to
Weiss, and their coworkers.18 The discovery of polyacetylene
provide a comprehensive review of the investigations conducted
and its high conductivity upon doping in by Shirakawa and
over the last decade in the development of conducting
coworkers in the 1970s further helped to advance the eld of
conductive polymers.19 Polypyrrole (PPy), polyaniline (PAni),
Peter Cass received his PhD in polythiophene (PTh), and poly(3,4-ethylenedioxythiophene)
polymer chemistry from Swin- (PEDOT) are most promising conducting polymers (CPs) for
burne University, Australia in use in biomedical applications.4,14,15,20,21 CPs exhibit electrical
2000. Peter did his Postdoctoral and optical properties similar to those of metals and semi-
Fellowship at Melbourne Univer- conductors, and offer advantages of conventional polymers
sity, Australia from 2001 to 2003. such as ease of synthesis.14,15,22 As an electrode for stimulation
He is currently working as and recording, conducting polymers are attractive due to the
Research Scientist at Common- possibility of chemical surface modication with physiologi-
wealth Scientic and Industrial cally active species to enhance the biocompatibility and the
Research Organisation, Mel- functionality of the electrodes.23,24 This unique combination of
bourne, Australia. His research properties makes CPs potential candidates for various
interests lie in polymer chemistry,
industrial polymers, adhesives, Pathiraja Gunatillake has a PhD
drug delivery and biomaterials. in polymer chemistry from the
City University of New York. He
joined CSIRO in 1988 and has
Mark Bown received the BSc successfully made the transition
degree in chemistry from Impe- from basic discovery research
rial College, London, U.K., and through the product development
the PhD degree from the Univer- pipeline, and contributed to
sity of Leeds, U.K., respectively. deliver products into the medical
He is currently the Team Leader device market. AorTech and Pol-
with the Industrial Innovation yNovo are two spin-off companies
Program, Commonwealth Scien- established from the technology
tic and Industrial Research developed under his leadership.
Organisation, Melbourne, Aus- He is a Fellow of the Biomaterials Science and Engineering (FBSE)
tralia, where he is responsible for and the American Institute of Medical and Biological Engineering
organic light-emitting diode (FAIMBE). He has received international recognition through tech-
research. nology innovations and literature contributions to the biomaterials
led and currently a Chief Research Scientist in CSIRO.
37554 | RSC Adv., 2015, 5, 37553–37567 This journal is © The Royal Society of Chemistry 2015
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biomedical applications such as biosensors, neural probes, (of the order of 20 nm), whereas powders or very thick lms are
neural prostheses, drug-delivery devices, tissue-engineering usually produced with chemical polymerization.14,17 Further-
scaffolds, and bio-actuators.4,14,15,20,21,25–31 more, electrochemical synthesis is limited to those systems in
The presence of conjugated double bonds (Fig. 2) along the which the monomer can be oxidized upon application of
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backbone gives rise to the conductivity in CPs.22 The p electrons potential to form reactive radical ion intermediates for poly-
in the conjugated backbone are available to delocalize into a merization.14 The common CPs (e.g. PPy, PTh, PAni, PEDOT)
conduction band and in the idealized situation of a uniform can be polymerized both chemically and electrochemically;
chain, the resulting conduction band would give rise to metallic however, several novel CPs with modied monomers can only
behaviour. However, such a system is unstable with respect to be synthesised using chemical polymerization.14,15
bond alternation, which causes the formation of an energy gap Table 1 presents the properties and electrical conductivity of
in the electronic spectrum.19 Dopant ions are introduced to the some conventional conducting polymers investigated for
Open Access Article. Published on 16 April 2015. Downloaded on 7/1/2025 11:26:52 PM.
structure to overcome the energy gap and hence, to impart biomedical applications.
conductivity to these polymers. The dopant ions carry charge in
the form of extra electrons to neutralise the unstable backbone
of the polymer in its oxidised state by donating or accepting 2.1 Polypyrrole (PPy)
electrons.18,19 On application of a potential across the CP lm, a Doped PPy has been the most thoroughly investigated
charge is passed through the lm as a result of a ux of ions conductive polymer for biomedical applications because of its
either in or out of the lm, dependent on dopant charge and high electrical conductivity, ease of preparation, and ease of
mobility, causing a disruption to the polymer backbone.18,19 CPs surface modication.17,20 PPy exhibits excellent environmental
can be doped with both p- and n-type dopants using a variety of stability and has been shown to have the ability to support cell
molecules, such as small salt ions (Cl, Br, or NO3), and adhesion and growth of a variety of cell types.40–42 PPy has been
larger dopants such as hyaluronic acid, peptides or explored for a number of biomedical applications including
polymers.14,20 tissue engineering,17,40 biosensors,26 drug delivery,43 and bio-
CPs can be synthesized either chemically or electrochemi- actuators.16,31,40,41,44,45 PPy can easily be synthesised in large
cally. Chemical methods of CP synthesis either use condensa- quantities at room temperature in a variety of common organic
tion polymerization or addition polymerization. While chemical solvents and also in water.46–49 The conductivity of PPy lms can
synthesis provides many different possible routes to synthesize be achieved up to 103 S cm1 depending on the type and
a variety of CPs and also permits the scale-up of these materials, amount of dopant.16,34–36 Due to its molecular structure, a
electrochemical synthesis is relatively straightforward and limitation of pure PPy is that once synthesised, it is hard to
hence, is most commonly used for making CPs.32,33 The process it further as it is crystalline, mechanically rigid, brittle
advantages of electrochemical synthesis include ease of and insoluble, making unmodied PPy poorly suited to most
synthesis, simultaneous doping and entrapment of molecules biomedical applications such as tissue engineering.16,17
during synthesis, however the lms are difficult to remove from Schmidt and coworkers reported the synthesis and physi-
electrodes and post-synthesis covalent modication of CP is cochemical characterization of poly(1-(2-carboxyethyl)pyrrole)
difficult.14 On the other hand, chemical synthesis offers more (PPyCOOH), a PPy derivative that contains a chemical group
options to modify CP backbone covalently and makes the post- that can be easily modied with biological moieties at the
synthesis covalent modication possible, although this method N-position of the polymer backbone, enhancing the biomate-
is oen more complicated.14 Another signicant difference rial–tissue interface and promoting desired tissue responses.50
between electrochemical and chemical methods of CP synthesis Human umbilical vascular endothelial cells (HUVECs) cultured
is that electrochemical method can produce very thin CP lms on PPyCOOH lms surface-modied with the cell-adhesive Arg-
Gly-Asp (RGD) motif demonstrated improved attachment and
spreading (Fig. 3).
In a study by Richardson and co-workers, PPy coated elec-
trodes were used for the delivery of charge and neurotrophins in
order to reduce the degeneration of spiral ganglion neurons
(SGNs) associated with cochlear implant use.43 The electrically
conducting polypyrrole/para-toluene sulfonate containing
neurotrophin-3 (PPy/pTS/NT3) was applied to cochlear implant
electrodes. The in vivo studies on guinea pigs showed the use of
the cochlear implant to deliver neurotrophic agents to SGNs in a
safe and controlled manner over the short-term, in addition to
electrical stimulation for enhanced preservation of SGNs aer
hearing loss.
There are a number of literature reports on the biocompati-
bility studies of PPy.44,51–54 A recent in vitro study has reported that
Fig. 2 Structures of common CPs investigated for biomedical PPy nanoparticles fabricated using oxidative polymerization
applications. route are cytotoxic at high concentrations.53 These nanoparticles
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Table 1 Conductivity and other properties of common conjugated conducting polymers used for biomedical applications
Polymer Conductivity (S cm1) Type of doping Properties Limitations Ref.
Polypyrrole 10–7.5 103 p High electrical conductivity, Rigid, brittle and 16, 34–36
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ease of preparation and ease insoluble
of surface modication
Polyaniline 30–200 n, p Diverse structural forms, Hard to process, 16, 35 and
environmentally stable, low cost non-biodegradable, 36
limited solubility
Polythiophene 10–103 P High electrical conductivity, Hard to process 16, 34–36
ease of preparation, good optical
property
Open Access Article. Published on 16 April 2015. Downloaded on 7/1/2025 11:26:52 PM.
Poly(3,4-ethylene 0.4–400 n, p Transparent conductor, Limited solubility 37–39
dioxythiophene) environmentally and electrochemically
stable
bridge across 10 mm sciatic nerve gap in rats. The regenerated
tissues were observed by electrophysiological and histological
techniques 24 weeks aer the operation. PPy extraction solution
showed no evidence of acute and subacute toxicity, pyretogen,
hemolysis, allergen, and mutagenesis, but there was a mild
inammation observed.
In summary, despite PPy's attractive properties and reports,
it is worth pointing out that the in vivo studies on PPy have been
limited and mainly focused on short term toxicity evaluation
only. Therefore, considering its drawbacks such as its poor
solubility and rigidity, more in vivo studies are required to
conrm the viability of PPy as a biomaterial.
2.2 Polyaniline (PAni)
PAni is the second most investigated conducting polymer with
many advantages such as its diversity of structural forms, high
Fig. 3 Typical fluorescent (top) and phase-contrast (bottom) images
of the labelled PPyCOOH films (A) and powders (B), the control PPy environmental stability, low cost and the ability to electrically
films (C), cells (HUVECs) on the RGD-grafted PPyCOOH films (D), and switch between its conductive and resistive states by doping/
on the control PPy films (E) cultured for 6 h at an initial density of dedoping process.20,55–58 It exists in various forms based on its
30 000 cells per cm2. Reprinted with permission from ref. 50, copy- oxidation level i.e. the fully oxidized pernigraniline base, half-
right 2006, American Chemical Society.
oxidized emeraldine base, and fully reduced leucoemeraldine
base.16,59,60 PAni emeraldine form is the most stable and
conductive.16,59 PAni is also difficult to process due to its poor
negatively affected the cell viability/proliferation, and this effect solubility in most of the available solvents.58
was directly dependent on the nanoparticle concentration. But In a study by Humpolicek and coworkers,61 both the non-
lower concentrations of PPy nanoparticles (<9.7 mg ml1) were conducting PAni (emeraldine base) and its conducting form
not found to affect cell viability/proliferation. The same group (PAni hydrochloride), were tested for their biocompatibility in
had also reported previously the results of an in vivo study terms of skin irritation, sensitization and cytotoxicity. The skin
showing that chemically synthesized PPy particles exhibited good irritation and sensitization testing was done in vivo, while
biocompatibility in mice over a 6 weeks period of treatment with cytotoxicity testing was performed in vitro on human immor-
these particles.51 Furthermore, in a study by Martin et al., PPy and talized non-tumorigenic keratinocyte and human hepatocel-
a synthetic peptide were co-deposited on an electrode surface by lular carcinoma cell lines. The results showed that both PAni
electrochemical polymerization.44 The stability of PPy/peptide hydrochloride and PAni base, have excellent biocompatibility
coatings was tested using in vitro soaking experiments whilst properties in terms of dermal irritation and sensitization.61
their effect on the brain tissue response and neural recording was However, both polymers showed considerable cytotoxicity,
examined in vivo. For in vivo studies, the electrodes were which was higher for PAni hydrochloride compared with PAni
implanted and evaluated for maximum of a 3 weeks period.44 The base. Furthermore, the polymer purication via reprotonation/
results showed that PPy/peptide coating promoted the neuron deprotonation cycle resulted in signicant reduction in cyto-
attachment and good recordings were obtained from the coated toxicity showing that the low molecular weight reaction residues
sites that had neurons attached. In another in vivo study,54 a PPy- or by-products, rather than PAni alone, are also likely to be
silicone tube was synthesized electrochemically and was used to responsible for observed cytotoxicity.
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The main challenge for using PAni and its derivatives for properties and dopamine delivery capacities were evaluated in vitro
biological applications arises from its poor cell compatibility, and in vivo.78 For in vivo studies, the PEDOT:PSS/dopamine coated
poor processibility, lack of exibility, and non-biodegrad- electrodes were implanted into brain striatum area of rats. The
ability.56,62 Nevertheless, PAni has been investigated for use in results demonstrated that the PEDOT:PSS/dopamine coatings on
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biomedical applications such as biosensors, neural probes, platinum electrodes could reduce electrode impedances, increase
controlled drug delivery, and tissue engineering applications charge storage capacities, and release signicant levels of dopa-
with promising outcomes.59,61 mine upon electrical stimulation of these electrodes. These results
indicated a potential application of PEDOT:PSS/dopamine-coated
implantable electrodes in the treatment of some diseases associ-
2.3 Polythiophene (PTh) and derivatives ated with dopamine decits, such as Parkinson's disease.78
Polythiophenes have properties similar to, and in some cases The use of biologically active dopants allows the CPs to have
Open Access Article. Published on 16 April 2015. Downloaded on 7/1/2025 11:26:52 PM.
superior to, those of PPy.63,64 Polythiophene and its derivatives features of a multiple stimuli responsive material, and hence
have been explored for electroactive scaffolds for cell culture, makes them more attractive as biomaterials for biomedical appli-
biosensors, and neural probes.65–68 Poly(3,4-ethylenedioxy- cations.42 In particular, electrical and biological cues are important
thiophene) (PEDOT) is considered the most successful PTh factors to include in interfaces with neurons for applications such
derivative due to its higher electrical conductivity and chemical as nerve conduits and neural probes. The incorporation of nerve
stability which allows its use in biomedicine and biotech- growth factor (NGF) as a co-dopant in the electrochemical depo-
nology.69,70 As compared to PPy and PAni, the investigations on sition of conductive polymers, PPy and PEDOT, has been evaluated
PEDOT are relatively recent. The biocompatibility of PEDOT has for its ability to draw forth specic biological interactions with
been well established.71,72 neurons.42,79 These studies revealed that PC12 (rat pheochroma-
PEDOT can be synthesized in various forms such as nano- cytoma) cells adhered to the NGF-modied substrate and extended
lms, nanorod arrays and nanober mats.73–75 Free-standing neurites on both PPy and PEDOT, indicating that the NGF in the
conductive ultra-thin nanolms based on PEDOT and poly- polymer lm is biologically active. This approach can be used to
styrene sulfonic acid (PSS) were fabricated by Mattoli and fabricate materials capable of both biological as well as electrical
coworkers using a process based on a modied supporting layer stimulation for biomedical applications.79
technique.73 The work demonstrated that the PEDOT:PSS
nanolms could be manipulated, folded and unfolded in water 2.4 Summary
many times without suffering from cracks, disaggregation or
from loss of conductive properties giving it potential applica- In summary, CPs have several attractive properties that include,
tions in the eld of sensing and actuation, as well as in the good stability, sufficiently high electrical conductivity, ability to
biomedical eld, e.g. as smart substrates for cell culturing and entrap, and release biomolecules. Furthermore, they can be
stimulation.73 The same research group also fabricated a potentially modied for electrical, chemical, physical, and
bending actuator by depositing a thin conductive polymer layer biocompatibility properties to better suit a specic applica-
of PEDOT:PSS over the surface of a polysiloxane-based mono- tion.14,15 However, their use in biomedical applications is limited
domain nematic liquid single crystal elastomer (LSCE) lm.76 because CPs are oen brittle and difficult to handle and the use
The mechanical properties of PEDOT:PSS, being better matched of larger dopants can further aggravate this effect.14,80 One way to
with LSCE than with metals or inorganic nanoparticles, allowed overcome the shortcomings of a CP is to use it together with
the development of an all-polymer reliable millimetre-scale another polymer in the form of a blend or composite in order to
actuating composite.76 Carmena and coworkers have explored combine the useful properties of both materials. The composites
the use of PEDOT (doped with PSS) coated microelectrodes for of CPs can provide the increased solubility and better mechanical
use as cortical neural prostheses.72 In vivo chronic testing of properties necessary for various biomedical applications without
microelectrode arrays implanted in rat cortex revealed that signicant compromise of their conductivity and other proper-
PEDOT coated Pt–Ir electrodes showed higher signal-to-noise ties as discussed in later sections.
recordings and superior charge injection compared to Pt–Ir
electrodes.72 In a study by Feng et al., PEDOT nanober mats 3. Conductive polymer composites
were fabricated by electrospinning combined with in situ
interfacial polymerization using FeCl3 as an oxidant.75 The 3.1 Composites/blends based on conjugated conducting
PEDOT nanober mats displayed good mechanical properties, polymers
exibility, and achieved an electrical conductivity of 7.8 0.4 S An effective way to improve mechanical properties of CPs is to
cm1 and similar biocompatibility to tissue culture plates.75 create their composites or blends with other polymers that have
Tarabella and coworkers employed organic electrochemical better mechanical properties for the intended application.
transistors (OECTs), based on the PEDOT:PSS, as sensors of Conducting polymers like PPy and PAni have also been explored
liposome-based nanoparticles in electrolyte solutions to assess as conductive llers, especially with natural polymers, in order
sensitivity and monitoring capabilities based on ion-to-electron to overcome the poor processability of these conducting poly-
amplied transduction.77 In an another study carried by Sui mers as well as to impart conductivity to otherwise insulating
et al., PEDOT:PSS coatings incorporated with dopamine were polymers.80–85 Doping with large molecules can also be used to
fabricated on platinum electrodes and their electrochemical prepare conducting polymer composites with improved
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mechanical properties. However, these processes unfortunately composite. The conductivity of a neat PAni sample was 3.0 S
may cause interference with electron conjugation within the CP cm1 and the sample with 7 : 1 ratio of PAni to collagen showed
due to the presence of insulating molecules.14 highest conductivity (0.27 S cm1) among the composite lms.
Ma and co-workers fabricated synthetic nerve conduits by The prepared composites showed a rather high percolation
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dip coating from PPy/poly(D,L-lactic acid) (PDLLA) composite threshold value while samples with PAni content lower than
solution obtained as a result of emulsion polymerization of ppy 50% in a collagen matrix did not show any measurable
in PDLLA solution. Aqueous FeCl3 solution was used to initiate conductivity. However, the PAni nanober–collagen composite
the oxidative polymerization.92 PC12 cells were used to assess lm was found to be well suited for cell culture and was claimed
the in vitro cell compatibility, which exhibited more and longer as a potential candidate for use as scaffold material for
neurites on composite than on PDLLA conduits aer being biomedical applications.86 Wallace and coworkers used vacuum
stimulated with 100 mV for 2 h. The 5% PPy/PDLLA composite vapour phase polymerization to produce conductive PEDOT
Open Access Article. Published on 16 April 2015. Downloaded on 7/1/2025 11:26:52 PM.
was also used to fabricate nerve conduits to bridge a 10 mm composites incorporated with triblock polymer poly(ethylene
defect in the sciatic nerve of a rat. Aer 6 months, the rats with glycol-propylene glycol-ethylene glycol) (glycol) for implantable
the PPy/PDLLA conduits showed functional recovery similar to devices.87 Iron(III) tosylate was used as an oxidant in the poly-
that of the gold standard autologous nerve gra and signi- merization. The PEDOT–glycol composites were found to have a
cantly better than that of the PDLLA conduits. The authors maximum conductivity of 1486 S cm1 being achieved at a
suggested that such a conduit can potentially be used in nerve glycol loading of 48 wt%. The results also indicated that cell
tissue regeneration eliminating the drawbacks associated with attachment and proliferation depended on the individual cell
using an autologous gra, including limited donor source, lines used and that the impact of glycol within the PEDOT
donor site morbidity, multiple surgery sites, and possible size composite was negligible.87
mismatch. Schmidt et al. synthesised conductive composites of PPy
Ferraz et al. prepared composites of nanocellulose and PPy using biologically active polysaccharide hyaluronic acid (HA) as
using FeCl3 as an oxidant and the effect of processing the dopant in order to create biomaterials for tissue engineering
parameters such as rinsing and extraction, as well as aging, on and wound-healing applications.80 These conductive, HA-
electroactivity and cytotoxicity was examined.95 These studies containing PPy lms retained HA on their surfaces for several
showed that while the composites need to be thoroughly days in vitro and promoted vascularisation in vivo and hence,
rinsed to remove impurities, reactants, and shorter oligomers were claimed as promising candidates for tissue engineering
to obtain a non-cytotoxic material, such processing has a and wound-healing applications benetting from both elec-
negative effect on the electrochemical ion exchange capacity trical stimulation and enhanced vascularisation. However, the
of the material. Aging of the PPy composites was also found to PPy/HA lms were more brittle, less conductive and exhibited a
have a pronounced negative effect on the biocompatibility of more nodular surface appearance when compared to PPy:PSS
the composite. In a recent study by Kobayashi and co-workers, lms. These differences were attributed to the diffusion limi-
conductive PPy-cellulose acetate lms were prepared from tations in the more viscous HA solution resulting in the inho-
cellulose acetate (CA) solution of pyrrole (Py) using wet cast mogeneous growth of the PPy/HA lms. In a similar study,96
methods.85 The PPy-CA composite lms containing different heparin (HE) was used as a dopant to simultaneously improve
concentrations of Py were prepared by casting a Py viscous the electrical stability and cell adhesion to PPy, because HE is
solution of CA on glass plate and immersing it in FeCl3 both a polyanion and an important glycosaminoglycan in cell
aqueous solution. The resultant composite lms showed membranes and extracellular matrix. PPy particles doped with
maximum electrical conductivity of 3.6 101 S cm1 with 4.7 HE were synthesized through emulsion polymerization using
wt% loading of PPy.85 In another study, composites of PPy and Fenton's reagent as an oxidant. Conductive biodegradable
chitosan with radical scavenger activity were produced for membranes of resistivity of 102 to 103 U sq1 were prepared
antioxidant applications in food packaging and biomedical from PPy (5% wt) with various amounts of HE and 95 wt%
applications.84 The composites were synthesized by the poly(L,L-lactide) (PPy/PLLA). The results showed that HE was
chemical polymerization of pyrrole in chitosan solution using incorporated into the PPy particles as counter ions and was
ammonium persulfate (APS) as the oxidant.84 In order to present on the particle surface. The conductive membranes
optimize the activity and stability of the composites, a range containing HE-doped PPy particles recorded enhanced elec-
of ratios of APS to PPy in composite was investigated. The trical stability, cell adhesion (human skin broblasts), and cell
FTIR and UV-Vis measurements identied an attachment of growth.
PPy to chitosan in the chitosan–PPy composites, which were Combining the characteristics of a conducting polymer such
formed as membranes (coatings) with conductivity in the as PPy with an elastomeric material, such as polyurethane (PU),
range of 107 to 103 S cm1. may yield a composite with electrical activity and signicantly
In an investigation by Kim et al., hybrid composites of PAni improved biocompatibility and mechanical resilience. A series
nanobers and collagen with various ratios of well dispersed of electrically conducting PPy nanoparticle and PU composites
PAni nanobers in a collagen matrix were fabricated.86 The PAni with different ratios were prepared by Broda et al. via an in situ
nanober-collagen composite lm, doped in HCl solution, polymerization of Py using FeCl3 as an oxidant in a PU emul-
remained electronically conductive, although conductivity sion.81 The polymerization resulted in a composite with a
decreased signicantly with decreasing amounts of PAni in the principle base of PU interspersed with an electrically
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percolating network of PPy nanoparticles. As the mass ratio of properties in both distilled water and electrolyte solution. In
PPy to PU increased so did electrical conductivity of the another study by Yang et al. reported the synthesis of a bacterial
composites. In addition, as the mass ratio of PPy to PU cellulose (BC)/PAni nanober composite which is an electro-
increased, the stiffness of the composite increased while the conductive hydrogel that may potentially be used for biosen-
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maximum elongation decreased. The PPy–PU composites sors and tissue engineering applications.88 The hydrogel was
exhibited elastomeric properties as well as conductivity, and synthesized in ammonium persulphate solution by in situ nano-
were shown to be cytocompatible with C2C12 myoblast cells. assembly of BC nanobers and PAni to enhance the electronic
The composite with ratio of 1 : 5 of PPy : PU was found to have conductivity of BC nanobers.88 The electrical conductivity of
the highest conductivity (2.3 106 S cm1) while the composite hydrogels was enhanced from 108 to 102 S cm1.
composite with ratio 1 : 100 was least conductive (1.0 1010 S Wallace and co-workers reported the synthesis of a single
cm1).81 Perez-Madrigal and co-workers prepared poly- component CP hydrogel for potential applications as tissue
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thiophene derivative/thermoplastic PU nanomembranes for engineering scaffolds.98 Poly(3-thiopheneacetic acid) hydrogels
tissue engineering applications.90 The conductivity values were fabricated by covalently crosslinking the polymer with 1,10 -
determined for the nanomembranes ranged from 5.19 106 carbonyldiimidazole. The hydrogels exhibited good swelling
to 2.23 105 S cm1.90 In another study, a polymer-based properties (with swelling ratios up to 850%) and the mechanical
stretchable electrode fabricated from a blend of PEDOT:PSS properties of the networks were found to be comparable to
and an aqueous polyurethane dispersion (PUD) was reported by those of muscle tissue. Hydrogels were found to be electroactive
Park and coworkers.93 The blend containing 73 wt% of non- and conductive at physiological pH. Fibroblast and myoblast
conductive PUD exhibited an electrical conductivity of 120 S cells cultured on the hydrogel substrates were shown to adhere
cm1. Ionic liquid(IL) based IL/PU/PEDOT:PSS composites were and proliferate.
fabricated by Okuzaki and co-workers by sandwiching the IL/PU Hybrid composites comprising of a conducting polymer and
gel between two conductive polymer lms made of PEDOT:PSS silver, have also been shown to achieve high conductivity.83
as so and exible electrodes.91 The electrical conductivity was These composites were produced mainly by the oxidation of
found to increase from 3.1 105 S cm1 to 8.8 105 S cm1 aniline or pyrrole with silver ions.99–101 However, high electrical
with increasing the IL content from 0 wt% to 40 wt%. conductivity (>1000 S cm1) of such composites is only achieved
Degradable polymers exhibiting conductivity have also with high amount of silver (>60%, w/w) and seems to be
recently gained considerable attention.15 The electrically con- controlled by percolation.83
ducting degradable polymers have been reported to improve Some relevant work on composites of CPs is summarised in
cell adhesion as well as proliferation and they could be used as Table 2.
scaffold materials for neural, cardiovascular, and bone tissue
regeneration for which electroactivity is important.15
PAni has been exploited for electroactive hydrogels which are 3.2 Composites of conductive nanoparticles/llers with non-
polymeric blends combining the responsive properties of elec- conjugated polymers
troactive polymers and highly hydrated hydrogels within an 3.2.1 Introduction. Electrical conductivity can be imparted
aqueous milieu that is hospitable to biological molecules such to insulating polymers by incorporation of conductive llers
as peptide sequences, enzymes antibodies, and DNA.97 The while still maintaining their polymeric characteristics.102
combination of hydrogels and inherently conductive electro- Carbon black, carbon ber, silver, and other metallic particles
active polymers allows both materials to retain their unique have oen been used as llers. Recently, nanosized conductive
responsive properties. In addition, the electroconductive llers including carbon nanotubes (CNTs), graphene, metal
hydrogels engender a new class of devices with low interfacial nanoparticles have generated a considerable interest and have
impedances suitable for neural prosthetic devices such as deep been explored extensively for the development of polymer based
brain stimulation electrodes, low voltage actuation for electri- conductive composites.83,103–111 The conductivity of such
cally stimulated drug release devices and potential for in vivo composites arises due to the formation of conductive paths of
biocompatibility in implantable biosensors. In a study, a highly ller particles within the polymer matrix.112 The formation of
swelling graed hydrogel composed of poly(acrylic acid) (PAA) conductive paths is governed by many factors such as the state
and polyvinyl alcohol (PVA) containing PAni nanoparticles were of dispersion, the geometry, the abundance and the intrinsic
prepared by in situ polymerization of aniline using ammonium properties of the nanollers. Moreover, the ller–matrix inter-
persulphate as an oxidant.89 This study mainly focused on the actions also play an important role in determining the electrical
synthesis and characterization of conductivity, swelling behav- properties of the nanocomposite. For these reasons, choosing a
iour, biocompatibility, and microhardness. Impregnation of composite preparation method that provides the desired level
polyaniline into PVA-g-PAA resulted in a composite hydrogel of ller distribution is of prime importance. The electrical
which showed electroconductive and electroactive behaviour. conductivity of a composite generally depends on the concen-
The electrical conductivity varied with varying content of PAni tration of conducting ller. At some critical loading known as
in the composite and was found in the range of 0.04–0.06 S percolation threshold (Fig. 4), the conductivity starts increasing
cm1 for 5% PAni content. The native and PAni impregnated by many orders of magnitude with very small increase in the
matrix not only showed a moderate biocompatibility and good ller loading. Aer the percolation threshold, the increase in
mechanical strength but also exhibited good swelling conductivity levels off and approaches that of the ller material
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Table 2 Properties of conjugated conducting polymer composites
Composite/blend Conductivity (S cm1) Properties Suggested applications Ref.
PPy/hyaluronic acid 3.08 103 Can support tissue growth Tissue engineering and 80
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and stimulate specic cell wound-healing applications
functions
PAni nanobers/collagen 0.27 Well suited for cell culture Scaffold material for 86
biomedical applications
PPy/chitosan 103–107 Radical scavenger Food packaging and 84
biomedical applications
PEDOT/glycol 1486 (maximum) — Implantable devices 87
PPy/cellulose acetate 6.9 104 to 3.6 101 — — 85
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PAni nanobre/bacterial 102 Hydrogel Biosensors, tissue 88
cellulose engineering
PAni nanoparticles/ 0.04–0.06 Hydrogel, biocompatible, — 89
poly(acrylic acid)/polyvinyl good mechanical strength
alcohol and good swelling properties
Polythiophene derivative/PU 2.23 105 Suitable for supporting Tissue engineering 90
electrically stimulated cell
growth
PEDOT:PSS/PU/ionic liquid 8.8 105 Mechanically exible, Actuating devices 91
stretchable
PPy/poly(D,L-lactic acid) 5.65 103 to 15.56 103 Nerve tissue regeneration (in Synthetic nerve conduits 92
vivo rat), biocompatibility
(PC12 cells)
PPy nanoparticles/PU 2.3 106 (maximum) Cytocompatible with C2C12 Tissue engineering 81
myoblast cells, elastomeric
properties
PEDOT:PSS/PU (aqueous 120 High pressure sensitivity Electronic skin sensor 93
dispersion)
PEDOT/RG-O 9.2 Good thermal and — 94
environmental stability
as described by percolation theory.112,113 It is at the percolation show superior mechanical, thermal and electrical properties as
threshold that the concentration of ller is enough to form a compared to the neat polymer.109,115 However, stable dispersions
continuous conductive network through the composite. It has of graphene in polar solvents can only be obtained using suit-
been found that the value of the percolation threshold able surfactants due to its hydrophobic nature.116,117
decreases with increasing aspect ratio (ratio of length to diam- Graphene oxide (GO) is similar to graphene but has the
eter) of the ller.102,113 oxygen containing polar functional groups which enhances its
Graphene is a two dimensional monolayer of sp2-hybridized biocompatibility, compatibility with polar solvents or with a
carbon arranged in honeycomb lattice and exhibits high polymer matrix.107,120–123 Incorporation of hydrophilic graphene
mechanical strength, electrical conductivity and ultra high based llers like GO also improves cell adhesion at the
specic surface area.114 Graphene based polymer composites biomaterials surface.122 CNTs are also carbon based llers
which are used for making electrically conductive nano-
composites. CNTs exhibit very good electrical conductivity of
>103 S cm1, with a high aspect ratio reaching 100–1000 for mm
long single-wall and multiwall CNTs.113,118,124 Apart from carbon
based conductive llers, metal nanoparticles have also been
explored to impart conductivity to non-conjugated insulating
polymers. Table 3 summarizes the various conductive llers and
their respective electrical conductivities.
One of the main challenges in the fabrication of carbon
based conductive polymer composites is that the carbon llers
are usually difficult to be homogenously dispersed within
polymer materials.125,126 Another challenge in fabrication of
conductive composites for biomedical applications is to achieve
both high conductivity and mechanical toughness at the same
time. The limiting conductivity is as important as the percola-
tion transition.102 The high conductivity is oen achievable at
Fig. 4 Conductivity of polymer composites as function of filler
concentration.
the cost of mechanical strength. It also seems fairly clear that
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Table 3 Electrical conductivity of various conductive fillers mixed with the polymer matrix in molten state.126 The thermo-
plastic polymer is mixed mechanically with ller at elevated
Conductive particles Conductivity of bulk material S cm1 Ref.
temperatures using conventional methods such as extrusion
Pt nanoparticles 105 102 and injection molding.132,133 The polymer chains are then
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Ni powders 105 102 intercalated between the ller particles to form nano-
Carbon nanotubes >103 118 composites. The polymer chains experience a signicant loss of
Graphene 104 119 conformational entropy during this process.113 Melt processing
is preferred for industrial-scale processes, because of its speed
and simplicity. This is also a preferred method for processing of
the direct use of nanosized materials does not provide a way to polymers which are unsuitable for solution mixing or for in situ
improve the making of conductive composite materials. polymerization.110
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However, if ller contact density can be reduced by sintering or 3.2.2.4 Latex technology. Apart from the above methods,
using high-aspect ratio llers, high conductivity can be ach- other methods have also been used by researchers to incorpo-
ieved.102,127,128 The following section describes the methods rate conductive llers into a polymer matrix in order to obtain
commonly used for the preparation of conductive polymer electrically conductive composites. Since the electrical
composites. conductivity arises from the formation of geometrical conduc-
3.2.2 Preparation methods of conductive polymer tion pathway, integration of individual graphene nanosheets
composites into well organized three dimensional assemblies and embed-
3.2.2.1 Solution mixing. The most common method used for ding them in polymer matrix is the key to achieve high
graphene and CNT based polymer composites is the solution conductivity.109,125 Latex technology is another method for
mixing because it facilitates separation of graphene sheets or making graphene and CNT based polymer composites and has
nanotube dispersion.113,123,129–131 By this method, a solution of advantages such as homogeneously dispersed llers in the
polymer is prepared and the nanoller is separately dispersed polymer matrix, easy processing and process up-scaling.109 In
in a suitable solvent by sonication (Fig. 5).113 For CNT/polymer this method, any ller that can be dispersed to yield an aqueous
composites, this step requires the employment of surface- colloidal dispersion can be used and similarly, any polymer that
modied nanotubes (either covalent or non-covalent) to ach- can be synthesized by emulsion polymerization or can arti-
ieve a metastable dispersion. Once the ller is dispersed in the cially be brought into the form of a polymer latex is suitable.109
solvent, the polymer, which was previously dissolved in the Latex technology facilitates direct incorporation of predomi-
same solvent, is added to the dispersion so that the polymer nantly individual nanollers into a highly viscous polymer
adsorbs on to the ller. The nal step is removing the solvent by matrix as well as it also allows the formation of three dimen-
evaporation. Both organic solvents and water have been used to sional framework of ller particles in polymer matrix.109,134 Latex
produce composites using this method. technology involves three main steps i.e. preparation of an
3.2.2.2 In situ method. In the in situ polymerization method, aqueous colloidal dispersion of the nanoller, mixing with a
the ller is rst swollen in the liquid monomer. A suitable polymer latex to form a two-component colloidal mixture and
initiator is then diffused and polymerization is initiated either drying (lyophilization) of the colloidal mixture in order to yield a
by heat or radiation.110 In situ polymerization is extensively used composite.109 Latex technology has been successfully used to
for the preparation of polymer/CNT composites due to an produce various CNT–polymer nanocomposites and graphene–
advantage of formation of a covalent bond between the CNT and polystyrene (PS) nanocomposites.109 The graphene–PS nano-
the matrix. The presence of polymeric chain onto the tubes' composites were prepared using latex technology with perco-
surface further facilitates their dispersion while providing a lation thresholds as low as 0.8 wt% and maximum conductivity
strong interface at the same time. This technique allows the values of 0.15 S cm1 for up to 2 wt% graphene loading.109 In
preparation of composites with high nanotube loading, which this work, it was also demonstrated that controlled clustering of
can be diluted by other techniques.113 the graphene ller favours the lowering of the percolation
3.2.2.3 Melt processing. Melt blending or melt processing threshold.
method has become attractive due to the advantage of being 3.2.3 Progress in conductive composites of non-conjugated
free of solvents. In this method, graphene or other nanoller is polymers. Most of the literature available on conducting
Fig. 5 Preparation of conductive polymer composites using solvent mixing.
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composites of non-conjugated polymers is very recent with
various conductive llers explored to impart conductivity to
polymers such as PS,115 poly(ethylene terephthalate) (PET),135
nylon136 and PU.15,113,137–140 The work is still in its infancy as
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researchers are still focusing more on fundamental work rather
than on applications. Polyurethanes (PUs) are of particular
interest to make conducting polymer composites by
introduction/incorporation of conductive particles because of
their biocompatibility, biostability, processability and good
mechanical properties.141,142 PUs include a wide variety of
materials ranging from thermoplastic elastomers to exible and
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rigid foams. Moreover, the polyurethanes nd application in
numerous medical applications such as vascular gras and
pacemaker lead insulators.113,131,141,143–145
For biomedical applications such as cochlear implants, a
polymer electrode with elastomeric mechanical properties and
metal like conductivity can offer a solution to overcome the
problems associated with electrical interfacing with neural
tissue.145 The following sections present the current progress in Fig. 6 SEM and TEM images of graphene–polystyrene composite. (a–
developing conductive polymer composites of non-conjugated d) SEM images of the microtomed composites reveal different
morphologies of the graphene sheets, including their packing, at
polymers with carbon and non-carbon conductive llers such different concentrations (vol%): (a) 0.24; (b) 0.96; (c) 1.44; and (d) 2.4.
as graphene, CNTs and metal nanoparticles. Scale bar, shown in (a) applies to (a–d). (e and f) High-resolution phase
3.2.3.1 Carbon ller based conductive polymer composites. contrast images and SAED patterns (inset) of (e) cast film made from
Ruoff and co-workers presented for the rst time a general powder composite, and (f) microtomed composite sample. The SAED
approach for the preparation of graphene–polymer composites patterns show the six-fold rotational symmetry expected for diffrac-
tion with the beam incident along [0001]. Adapted from ref. 115.
via complete exfoliation of graphite and molecular-level
Reprinted by permission from Macmillan Publishers Ltd: Nature,
dispersion of individual, chemically modied graphene sheets 442(7100), 282–286, copyright 2006.
within polymer matrix (Fig. 6).115 A PS–graphene composite
formed by this route exhibited a percolation threshold of 0.1
matrix.133 In a separate study, a nanocomposite paper was
vol% for room temperature electrical conductivity. At only 1
prepared from reduced graphene oxide sheets (rGO) and amine-
vol%, this composite exhibited a conductivity of 0.001 S cm1.
modied nanobrillated cellulose (A-NFC).146 Various rGO/A-
Luo et al. reported the preparation of composite of PET resin
NFC nanocomposites with varied content of graphene (0.1–10
and CNTs by melt compounding using a twin-screw extruder.135
wt%) were obtained. The rGO/A-NFC nanocomposites exhibited
The composites with 4 wt% loading of CNTs exhibited a volume
an electrical percolation threshold of 0.3 wt% with an electrical
electrical resistance of 103 U cm, 12 orders of magnitude lower
conductivity of 4.79 106 S cm1 and a conductivity of 0.72 S
than that of pure PET. Scanning electron microscopy (SEM)
cm1 with 10% graphene loading. The composite showed
micrograph showed well dispersed CNTs in PET matrix
improved tensile strength when compared to neat cellulose and
although optical microscopy micrograph showed discontinuity
graphene oxide paper, demonstrating an excellent reinforce-
of conductive phase existed in some segments of the composite
ment of graphene sheets.
bre. The rheological behaviour of PET/CNTs composites
PU-based composite lms containing highly aligned gra-
showed that PET/CNTs composites containing high nanotube
phene sheets were produced through an environmentally
loadings exhibited a large decrease in viscosity with increasing
benign process developed by Kim and coworkers.138 An aqueous
shear frequency. A composite ber was prepared using the
liquid crystalline dispersion of graphene oxide was reduced in
conductive PET/CNTs composites and pure PET resin by a
situ in PU, hence producing a ne dispersion and a high degree
spinning process and a cloth was woven from the composite
of orientation of graphene sheets. The electrical conductivity of
ber and common terylene (composition 1 : 3). The cloth
the composites was measured in the in-plane direction (surface
showed good anti-static electricity property with a charge
conductivity) as well as in the through-the-thickness (or
surface density of 0.25 mC m2.
perpendicular) direction (volume conductivity). The conductiv-
In another study on PET, Yu and co-workers prepared PET/
ities of the composites containing 0.5 wt% graphene were of the
graphene nanocomposites by melt compounding which resul-
same order of magnitude and almost identical in the in-plane
ted in a sharp transition of PET from electrical insulator to
and perpendicular directions, showcasing an isotropic behav-
semiconductor with a low percolation threshold of 0.47 vol%.133
iour and conrming homogeneous and random dispersions of
Furthermore, the electrical conductivity of 2.11 102 S cm1
GO. However, by increasing the graphene content to 2 and 5
was achieved with 3.0 vol% loading of graphene. The low
wt%, there was several orders of magnitude of difference
percolation threshold and improved electrical conductivity were
between the conductivities in two directions. The conductivity
attributed to the high aspect ratio, large specic surface area
in the in-plane direction was signicantly higher (103 S cm1, 4
and uniform dispersion of the graphene nanosheets in PET
37562 | RSC Adv., 2015, 5, 37553–37567 This journal is © The Royal Society of Chemistry 2015
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wt% ller loading) than that measured through the thickness scaffolds for bone regeneration, tissue engineering and nerve
(1.7 108 S cm1). The signicant anisotropy in electrical regeneration.150–158
conductivity in composites with high graphene contents was 3.2.3.2 Non-carbon ller based conductive polymer compos-
attributed to alignment of graphene sheets so that conductive ites. Metal nanoparticles have been also investigated as
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networks are preferentially formed along the plane direction conductive llers to prepare conductive polymer composites.
whereas fewer conductive paths are present in the bulk. In Kotov and co-workers demonstrated the fabrication of stretch-
another attempt by Cho et al.,139 highly exible, conductive, and able conductors of PU containing spherical gold nanoparticles
shape memory polyurethane nanocomposites were prepared for deposited by either layer-by-layer assembly or vacuum-assisted
potential applications as materials for actuators, electronics occulation.149 High conductivity and stretchability were
and articial muscles. Composites were prepared using both observed in both composites despite the minimal aspect ratio of
graphene and CNTs as conductive llers and their effect on the nanoparticles. These materials achieved electrical conduc-
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electrical and thermal conductivity of the composite was tivities of up to 11 000 S cm1 and also demonstrated the
examined. CNTs and functionalized graphene sheets were electronic tunability of mechanical properties resulting from
incorporated as crosslinkers in the prepolymer. In comparison dynamic self-organization of the nanoparticles under stress.
to pristine PU and CNT-crosslinked PU composite, the In another study, Pei et al. fabricated an elastomeric trans-
graphene-crosslinked PU composite exhibited better mechan- parent composite electrode comprising a percolation network of
ical properties. The graphene-crosslinked PU composite also copper nanowires (CuNWs) embedded in the surface layer of an
showed a higher electrical conductivity (1.67 103 S cm1) elastomeric PU matrix.140 The composite electrode was fabricated
than the CNT-crosslinked PU composite (2.30 104 S cm1). by rst forming a highly conductive CuNW network on glass, then
The composites also exhibited good shape recovery, shape overcoating with a layer of a liquid polyurethane precursor which
retention and fast electroactive shape recovery rate. was subsequently polymerized, and nally peeling off the result-
In a more recent study by Yang and coworkers, graphene ing PU sheet. The composite retained the elastomeric stretch-
incorporated polystyrene nanocomposites were prepared by ability of the polymer matrix. Pre-treatment of the CuNW network
integrating electrostatic self-assembly and latex technology.125 with 6-aminohexanoic acid enhanced the bonding between
Positively charged polystyrene was synthesized rst via disperse nanowires and PU matrix, and signicantly improved the revers-
polymerization using a cationic co-monomer and then was ibility of the surface conductance of the composite electrode
directly co-assembled with graphene oxide. A honeycomb like during repeated stretching at room temperature.
graphene three dimensional framework was embedded in An overview of properties and applications of conductive
polystyrene matrix aer in situ chemical reduction and hot composites of non conjugated polymers is provided in Table 4.
compression molding. The resultant nanocomposites showed In summary, conductive composites of CPs have been
extremely low percolation threshold of 0.09 vol% and a explored in order to overcome their insolubility, brittleness and
conductivity of 0.252 S cm1 at ller content of 1.22 vol%. This low processability, while retaining their biological properties
study demonstrated the use of integrating two methods to such as cell adhesion. Most of this work has focussed on
obtain composites with well-organised three dimensional biomedical applications and these studies have demonstrated
microstructures and hence, better electrical conductivity. that the electrical conductivity of CPs is usually compromised at
In another very recent study, Jeong and coworkers examined the expense of mechanical properties. On the other hand, the
the effect of extended thermal treatment to improve the work on conductive composites of non conjugated polymers is
conductivity of graphene loaded composites.136 Moderately relatively recent and more focussed on understanding the
functionalized graphenes were used to prepare electro- fundamentals such as impact of different conductive llers and
conductive graphene/nylon 6 composites with a low percolation their loadings. While the initial work on non conjugated poly-
threshold of 0.39 wt% and an electrical conductivity of 6.84 mer composites was based on conventional (non-biomedical
104 S cm1 for a low carbon incorporation of 0.54 wt%.136 The polymers) such as PS, PET and nylon. In more recent work,
functionality of the graphenes was modulated by the thermal conductive composites of polyurethane and biocompatible
reduction time and the graphitic structure of graphene was natural polymers have been investigated for biomedical appli-
strengthened by extended thermal treatment. It was observed cations. Amongst the organic llers, graphene is a more popular
that the main strengthening mechanism in the rst 5 min was choice as conductive ller due to its high conductivity and ease
the generation of new sp2 domains followed by the growth of of incorporation. The ultimate goal is to achieve reasonable
the domains during the next 5 min. This extended thermal electrical conductivity with lowest possible amount of conduc-
treatment improved the conductivity of the graphene itself as tive ller, while retaining the properties of host polymer. The
well as the composite loaded with graphene. However, it led to a major challenges thus lie in selection of conductive ller,
poor dispersion of graphene in the composites, reduced crys- achieving low percolation threshold and retaining biocompati-
tallization of nylon 6 and reduced reinforcement of nylon 6 by bility for biomedical applications.
graphene.136
Furthermore, there are various reports found in literature on 4. Conclusions and future prospects
use of CNTs as conductive ller to make conductive polymer
composites for various biomedical applications such as The review was focused on assessing the level of understanding
of the potential of conducting polymers for biomedical
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Table 4 Properties of conductive composites of non-conjugated polymers
Conductivity
Composite/blend Loading of ller Method of fabrication (S cm1) Properties Applications Ref.
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Polystyrene/graphene 2.5 vol% Solution mixing 1 Good electrical — 115
conductivity
Polyethylene 3 vol% Melt compounding 2.11 102 Enhanced electrical Electromagnetic 133
terephthalate/graphene conductivity interference (EMI)
shielding devices
Polyethylene 4 wt% Melt compounding 103 Anti-static electrical — 135
terephthalate/CNT property
Cellulose/graphene 10 wt% Solution mixing 0.72 Enhanced mechanical Portable and bendable 146
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nanocomposite paper and electrical properties electronic equipment,
EMI shielding devices
and electromagnetic
pulse protection
Nylon 6/graphene 0.54 wt% In situ polymerization 6.84 104 Enhanced electrical — 136
conductivity
Polystyrene/graphene 1.22 vol% Electrostatic assembly 0.252 Enhanced electrical — 125
nanocomposites integrated latex technology conductivity
PU/graphene 2 wt% In situ polymerization >103 Shape memory — 147
properties
PU/graphene 4 wt% In situ polymerization 1.67 103 Shape memory Actuating devices, 139
properties articial muscles
PU/rGO (4%) 4 wt% Solution mixing 103 Enhanced electrical — 138
conductivity
Waterborne PU/acid 1.5 wt% In situ polymerization 1.1 103 Enhanced thermal, Waterborne coatings 148
treated CNT conductive, and
antistatic properties
PU/CNT 4 wt% In situ polymerization 2.30 104 — Actuating devices 139
PU/CuNW — In situ polymerization — Low sheet resistance Stretchable electrodes 140
of <102 U sq1,
elastomeric, transparent
PU/AuNP 21.7 vol% Layer by layer deposition Up to 1.1 104 High electrical Stretchable conductors 149
and vacuum-assisted conductivity, exible in medical,
occulation optoelectronics, and
energy storage devices
applications based on many literature reported studies over the another area that these materials may nd applications, mainly
last decade. Most of the early studies have been focussed on as substrates for regeneration of tissues where electrically
evaluating the suitability of well known conducting polymers conductivity can enhance cell growth. However, the area is full
for biomedical applications. The limitations of conducting of unresolved technology challenges providing researchers with
polymers, such as low processability, poor mechanical proper- opportunities for further research and development work.
ties and biocompatibility, have prompted researchers to explore
various chemical modication techniques, and blending with
conducting nanoparticles and non-conducting polymers to Acknowledgements
overcome these limitations. The importance of the choice of
The authors would like to acknowledge the nancial support
conducting particles combined with appropriate blending
provided by CSIRO Office of Chief Executive Postdoctoral
techniques appear to be the key to develop useful composites
Program.
that may nd applications in biomedical implants. While this
approach may help address processability, mechanical proper-
ties and biocompatibility, the improvement will come with
some compromise in electrical conductivity, limiting the range
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