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Conducting Ink Based on Cellulose Nanocrystals and Polyaniline for

Flexographical Printing

Article  in  Journal of Materials Chemistry C · November 2017

DOI: 10.1039/C7TC03729E

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 Journal of
Materials Chemistry C
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Conducting ink based on cellulose nanocrystals

and polyaniline for flexographical printing†
Cite this: DOI: 10.1039/c7tc03729e
Published on 03 November 2017. Downloaded by RSC Internal on 21/11/2017 11:16:01.

R.-M. Latonen, *a A. Määttänen, ‡b P. Ihalainen, §b W. Xu,c M. Pesonen,d

M. Nurmie and C. Xuc

A water-based environmentally friendly electrically conducting ink composed of cellulose nanocrystals

Received 16th August 2017,
Accepted 2nd November 2017
DOI: 10.1039/c7tc03729e
rsc.li/materials-c
(CNC) and polyaniline (PANI) was prepared. PANI was synthesized by the emulsion polymerization
approach using dodecylbenzenesulfonic acid (DBSA) as the dopant to induce spherical nanoparticulate
formation. Glycerol was used to adjust the viscosity of the ink. The CNC–PANI ink was characterized by
transmission electron microscopy, UV-visible spectroscopy and viscosity measurements. The ink was
successfully printed on multilayer curtain coated paper by the flexographical printing method. The
printed layers were characterized by optical and atomic force microscopy techniques and cyclic
voltammetry. A stable nanoparticulate CNC–PANI ink with an electrical conductivity of the printed films
between 30 and 60 S cm 1 was obtained which was more than an order of magnitude higher than for
the corresponding film without CNC.

1. Introduction unstable metals in air.1 Conductive inks based on carbon

In printed electronics conventional printing processes are
implemented to deposit mainly conductive, semi-conductive
or dielectric inks on flexible substrates (plastics, metallic foil,
paper, nanocellulose) for manufacturing of functional struc-
tures for use in e.g. transparent electrodes, RFID tags, electronic
paper, implantable medical devices, thin film transistors, light
emitting devices and solar cells.1–5 Conventional printing tech-
niques are good candidates for fast, cheap and eco-friendly
manufacturing of electronic devices. However, the conductive
inks used nowadays often require post-printing processes such
as sintering1,3,6 and are composed of expensive noble metals or
a
Johan Gadolin Process Chemistry Centre, Laboratory of Analytical Chemistry,
Faculty of Science and Engineering, Åbo Akademi University, Biskopsgatan 8,
20500 Turku/Åbo, Finland. E-mail: rlatonen@abo.fi
b
Center for Functional Materials, Laboratory of Physical Chemistry, Faculty of
Science and Engineering, Åbo Akademi University, Porthansgatan 3-5,
20500 Turku/Åbo, Finland
c
Johan Gadolin Process Chemistry Centre, Laboratory of Wood and Paper
Chemistry, Faculty of Science and Engineering, Åbo Akademi University,
Porthansgatan 3, 20500 Turku/Åbo, Finland
d
Center for Functional Materials, Physics, Faculty of Science and Engineering,
Åbo Akademi University, Porthansgatan 3, 20500 Turku/Åbo, Finland
e
Center for Functional Materials, Laboratory of Paper Coating and Converting,
Faculty of Science and Engineering, Åbo Akademi University, Porthansgatan 3,
20500 Turku/Åbo, Finland
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c7tc03729e
‡ Current address: Saule Technologies, Wrocław Technology Park, 11 Dunska
Str., Sigma building, 54-427 Wrocław, Poland.
§ Current address: MetGen Oy, Rakentajantie 26, 20780 Kaarina, Finland.
nanotubes (CNTs) and graphene suffer from agglomeration
requiring chemical modification usually decreasing their elec-
trical conductivity and the use of graphene oxide, on the other
hand, requires post-printing reduction to regain the electrical
properties of graphene.1,2 The use of printing technology
together with water-based ink formulations allow the produc-
tion of more environmentally friendly electronic devices. In
particular the flexographic printing method used in this study
allows the use of a variety of printing inks and printing
substrates, is a high-speed printing method and significantly
cheaper than other printing methods. Furthermore, printing on
a paper substrate increases the ecological value of the end-
product which is an important issue towards a more sustain-
able world. The decreased market for more conventional paper
products has also raised the need for new application demands
on paper. Paper as a substrate is also less demanding in respect
of the ink.
Nanocellulose is a strong candidate to form both free-
standing and biodegradable substrates3–7 and ink formulations
for printed electronics.3,9–11 Due to its nanoscale dimensions,
high surface area, low density, outstanding mechanical proper-
ties, sustainable availability, renewability, ability to form free-
standing transparent films and suspension stabilizing ability
nanocellulose has found wide application potential in several
fields ranging across automotive, construction, packaging,
paper, aerospace, paint, cosmetics, pharmaceuticals, sensors
and optical and electronic devices.12,13 In particular the dispersing,
stabilizing and binding abilities of nanocellulose are useful
properties in conductive inks.3 However, until now only very

This journal is © The Royal Society of Chemistry 2017 J. Mater. Chem. C


Paper
few nanocellulose-based electrically conducting inks have been
developed. Koga et al. utilized the reinforcing and nanodisper-
sing properties of cellulose nanofibrils (CNF) to provide con-
ductive and inkjet printable inks consisting of CNTs11 and
Hoeng et al. have studied the printability of conductive
CNF–Ag inks on nanocellulose coated cardboard.9 Tang et al.
have prepared a photoelectric ink based on CNF and CdS
quantum dots where CdS quantum dots acted as the pigment
and CNF as the binder.10 In this study we have developed an
electrically conducting ink based on the electrically conducting
polymer (ECP) polyaniline (PANI) and cellulose nanocrystals
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(CNC) for flexographical printing.
ECPs having intrinsic conductivity in the metallic or semi-
conducting regimes are well-known to possess several properties
such as tunable electrical conductivity, optoelectronic properties,
easy preparation and variable morphology useful in a broad
range of applications.14–16 PANI is one of the most widely studied
ECPs which is conducting and stable in its emeraldine salt (ES)
form in acidic solutions.14 After the chemical or electrochemical
synthesis of PANI, the polymer, however, usually exists in powder
or insoluble film form with poor mechanical properties which
makes it difficult to process.16 PANI doped with poly(styrene
sulfonate) (PSS),17 trifluorosulfonic acid and camphorsulfonic
acid18 solubilised in dimethylsulphoxide (DMSO) have also been
used as an ink for the fabrication of inkjet printed tracks
showing a negative capacitance effect attractive in high-
frequency applications. Additionally, PANI synthesized by using
ferric chloride as an oxidizing agent and a co-dopant dissolved
in DMSO and ink-jet printed on a plastic sheet has shown
properties applicable in neuromorphic devices.19
Formation of composites of ECPs and nanocellulose affords
combing the electrical conductivity of ECPs and the mechanical
strength and processability of nanocellulose. As a result, the
processable nanocomposites of PANI and nanocellulose, both
CNF and CNC, have successfully been made.20–22 Nanocellulose
acted as a platform and stabilizer for the formation of stable
PANI suspensions and to increase the film formation capability.
These films, however, had rather low electrical conductivities (s)
of between 1.0  10 2 and 1.7  10 1 S cm 1 depending on the
PANI loading in nanocellulose. One reason for the relatively low
conductivity values obtained in these films could be incomplete
doping during the polymer synthesis. In addition, the nature of
the dopant has an effect on the composite morphology and its
conductivity, as well as the aniline : oxidant molar ratio used
during polymerization affects the conductivity of the films.
The electrical conductivity of PANI may be increased by using
the dispersion polymerization approach and suitable solvents
compared with other chemical and electrochemical polymeriza-
tion means. This is due to the formation of spherical nano-
particles which form a brush-like chain morphology with
gradual disorganization during continuous film growth leading
to an increased delocalization of the p-electrons.23 Highly con-
ducting PANI with electrical conductivities from 15 S cm 1 to
200 S cm 1 have been prepared in the presence of dodecyl-
benzenesulfonic acid (DBSA) micells,24 camphorsulfonic acid25
and poly-N-vinylpyrrolidone, sodium dodecylsulfate, Tween 20
J. Mater. Chem. C
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Journal of Materials Chemistry C
and Pluronic F108.26 Treatment with concentrated H2SO4 has
been shown to increase the electrical conductivity of poly(3,4-
ethylenedioxythiophene) (PEDOT) doped with PSS (PEDOT:PSS)
films significantly and conductivities up to 44000 S cm 1 have
been achieved.27 However, this technique suffers from several
drawbacks such as difficulties in washing the acid from the
polymer matrix, and the oxidizing and dehydrating nature of
H2SO4 may destroy the used paper or plastic substrate, as well as
the high cost of the treatment and safety and environmental
problems. Therefore, other methods using mild acid treatments
have also been proposed.28 The applicability of these methods in
printed electronics is, however, limited because they involve extra
liquid-based post-printing thermal treatment and washing steps.
Different printing methods have been used to deposit con-
ductive PANI or PANI-based composite films on a paper substrate,
including screen printing, inkjet-printing and flexographic
printing.29–31 However, from the mass-manufacturing perspective,
flexographic printing offers the most attractive option due to the
high-volume and low-cost characteristics of the technique.32
The aim of this study was to develop a water-based envir-
onmentally friendly and highly conducting ink suitable for the
flexographical printing method. For this reason water and
glycerol were chosen as the solvents. Glycerol has been found
to assist the synthesis of spherical nanosized polypyrrole (PPy)
particles and to act as a stabilizer hindering precipitation of the
polymeric particles.33 Glycerol used as the polymerization
medium compared with water has also been shown to increase
the electroactivity of the prepared PPy film. In other studies
glycerol has been found to significantly affect the conductivity
of PEDOT:PSS34 and to act as a plasticizer highly increasing
the chain mobility of PEDOT:PSS in inks and improving the
viscosity, surface wetting properties, surface morphology,
and avoiding nozzle clogging problems and improving heat
resistance during inkjet printing.35,36
In the present work a CNC–PANI ink in a water-glycerol
solvent system has been developed. To our knowledge an ECP
and CNC based conductive ink has not been reported earlier.
The water-based ink has been characterized by transmission
electron microscopy (TEM), UV-visible spectroscopy and visc-
osity measurements. After flexographic printing on the curtain
coated paper the surface coverage and nanoscale topography of
the prints have been studied by optical and atomic force micro-
scopy techniques. The electroactivity and the electrical conduc-
tivity of the prints have been determined by cyclic voltammetric
(CV) and 4-point probe measurements, respectively.
2. Experimental
2.1 Materials
The cellulose nanocrystals (CNC) used in this study were
prepared by sulfuric acid hydrolysis. Briefly, bleached chemical
pulp (birch) was hydrolyzed with sulfuric acid (64 wt%) at 25 1C
for 0.5 h. Then, the suspension was diluted by using distilled
water with ten-fold volume of the acid solution to terminate the
reaction, and left to sediment. The clear supernatant phase was
This journal is © The Royal Society of Chemistry 2017

Journal of Materials Chemistry C
decanted off and the remaining CNC phase was recovered by
centrifugation (3500 rpm, 10 min). After centrifugation, the
CNC phase was transferred to dialysis tubes (12–14 kDa) and
dialyzed against deionized water for several days until the pH
value and conductivity became constant. The suspension was
dispersed using an ultrasonic bath for 15 min to give a better
dispersibility.37,38 The obtained 0.51 wt% CNC suspension was
stored in a refrigerator at 4 1C for further use.
Aniline was obtained from Sigma-Aldrich (499.5%) and
distilled before use. Ammonium persulfate (APS, 98+%) used
as an oxidizing agent during the polymerization of aniline,
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dodecylbenzenesulfonic acid (DBSA, 70 wt% solution in
2-propanol) and glycerol (99%) were obtained from Sigma-
Aldrich and used as received. Hydrochloric acid (37–38%) was
obtained from J. T. Baker. Deionized water (resistivity ca. 18 MO
cm) was used throughout this work.
A multi-layer curtain coated (MLCC) paper (Metso, Finland)
was used as a printing substrate.39 MLCC paper has been
specially developed for printed electronics and has excellent
barrier properties against water and solvent penetration and
contains components normally used in paper-making.40 Here,
an uncalendered version was utilized in flexographic PANI
printings. For CV measurements MLCC substrates with inkjet-
printed gold electrodes were used. The gold nanoparticles
(15 wt%) were dispersed in xylene (Sigma-Aldrich). Inkjet print-
ing of the gold ink was performed with a Dimatix Materials
Printer (DMP-2800, FUJIFILM Dimatix, Inc. Santa Clara, USA).
The printing was done under ambient conditions using a single
nozzle, 10 pL drop volume, 27  3 V firing voltage, 20 mm drop
spacing and a custom waveform to ensure optimal droplet
formation.
2.2 Preparation of the ink
For the preparation of the ink the obtained 0.51 wt% CNC
suspension was diluted with deionized water to 0.2 wt% and
consequently with glycerol to obtain a 1 : 1 (v : v) mixture. The
CNC content in the reaction mixture was then 0.1 wt%. To this
solution 0.08 M APS and 0.19 M DBSA was added and well-
stirred. Finally 0.16 M aniline was added receiving a molar ratio
aniline/APS of 2. The polymerization was left to proceed for at
least 2.5 h under magnetic stirring. As a reference sample a
PANI ink without CNC was prepared in a 1 : 1 (v : v) water/
glycerol solution in the same manner as the CNC–PANI ink
described above.
2.3 Flexographical printing
Five and ten layers of both the CNC–PANI and PANI inks were
printed on the MLCC paper. Flexographic printing of the
polymeric coating layers was carried out with a laboratory scale
printability tester (IGT Global Standard Tester 2, IGT Testing
system, the Netherlands). The ink was applied to a small area of
the anilox roll behind the doctor blade. During printing the ink
is transferred onto the anilox roll engraved with thousands of
small cells. The volume of the cells on the anilox roll defines
the amount of ink that is transferred onto the printing plate
containing a relief pattern. The excess ink from the anilox roll is
This journal is © The Royal Society of Chemistry 2017
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removed by the doctor blade. When the printing starts, the
anilox roll accelerates to its printing speed and rotates to
distribute the ink, simultaneously as the printing plate and
impression roll rotate through one revolution to transfer the
ink onto the substrate. In this study, printing was carried out at
23 1C and 50% RH. The amount of ink was controlled by an
anilox roll having a cell angle of 451, a cell volume of 20 ml m 2
and a line count of 40 l cm 1. A patterned photopolymer plate
(Ohkaflex, Espoon Painolaatta, Finland) was utilized to transfer
the ink to the printing substrate. The pressure between the
anilox roll and the printing plate was 100 N, while the pressure
between the printing plate and the substrate was 50 N. The
printing speed was 0.5 m s 1.
2.4 Characterization of the ink
The bulk morphologies of CNC, PANI ink and the CNC–PANI
ink were studied by TEM. The dried suspensions of CNC and
CNC–PANI were analyzed on thin holey carbon reinforced
Formvar films and negative staining with 1% uranyl acetate
was used to increase the contrast in the micrographs. The PANI
reference sample was analyzed on a thin graphene oxide
support. A JEOL JEM-1400 Plus TEM instrument operated at
80 kV was used for imaging.
The UV-visible spectra of the developed inks were measured
from solutions of 25 ml of sample diluted with 2 ml 0.01 M HCl
to have a pH of around 2. The background spectrum for the
CNC–PANI ink was recorded from 25 ml of CNC/glycerol
solution (1 : 1) diluted with 2 ml 0.01 M HCl and for the PANI
ink without CNC from 25 ml of water/glycerol solution (1 : 1)
diluted with 2 ml 0.01 M HCl. The spectra were measured
between 300 and 1100 nm with a scan rate of 480 nm min 1 on
a Perkin-Elmer Lambda 25 spectrophotometer by using a 1 cm
path length quartz cuvette.
The rheological behavior of the developed inks was studied
using a modular compact rheometer MCR 300 (Anton Paar).
The measurements were performed with a cone and plate
geometry and the measurement gap was 0.05 mm. A logarithmic
ramp with a shear rate varying from 0.01 to 1000 s 1 was
performed to monitor the ink dynamic viscosity (m).
2.5 Characterization of the printed layers
A NTEGRA Prima (NT-MDT, Russia) atomic force microscope
(AFM) coupled with an optical light microscope was used for
analyzing the surface coverage, topography, thickness and
roughness of the printed films. The microscope was placed
on an active vibration isolation table (TS-150, Table Stable Ltd,
Switzerland), which was further placed on a stone table to
eliminate external vibrational noise. Topographical imaging
was carried out by means of an intermittent-contact mode
under ambient conditions (RH = 26  4%, RT = 26  2 1C)
using rectangular cantilevers (Model: NSG01, NT-MDT, Russia) with
a nominal tip radius of 10 nm. The images (1024  1024 pixels)
were recorded in the repulsive regime using a damping ratio of
0.6–0.7 and a scan speed of 0.3–0.7 Hz. AFM Images were
processed and analyzed with the Scanning Probe Image Processor
software (SPIPt, Image Metrology, Denmark). A roughness
J. Mater. Chem. C

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analysis of the samples was conducted by using AFM with an image
size of 5 mm  5 mm. The root-mean-square roughness (Sq) and the
surface area ratio (Sdr) were calculated to quantify the surface
topography. Sdr describes the roughness-induced increment of
the interfacial surface area relative to the project flat plane.
CV characterization of the printed layers was done in a three-
electrode one-compartment electrochemical cell using an Autolab
PGSTAT100 potentiostat with GPES software. For CV analysis two
stripes of gold were printed on top of the MLCC paper41 between
which the CNC–PANI and PANI inks were printed. These Au
stripes were connected together with Ag paste (Electrolube) and
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used as the working electrode. A printed Ag stripe on the MLCC
paper39 was used as the counter electrode and a Ag/AgCl/KCl (3 M)
electrode served as the reference electrode. The CV measurements
were performed in 2 ml 0.1 M HCl by cycling the potential
between 0.4 and 0.5 V with the scan rates of 10, 20, 50 and
100 mV s 1. The background electrolyte solution was purged with
N2-gas for 10 min before the CV measurements. The back of the
MLCC paper electrode was covered with polydimethylsiloxane
(PDMS, Wacker Chemie) cross-linked at 160 1C for a few minutes
in order to prevent water diffusion through the paper.
The electrical conductivity of the printed layers was measured
with a 4-point probe method in a linear configuration having a tip
spacing of 1.82 mm. The tips are spring-loaded gold needles with
a tip curvature corresponding to a circle diameter of 60 mm. The
measurements were carried out on a non-conducting Teflon
surface. A suitable bias current of 10 8 to 5  10 7 A was applied
over the layers and the corresponding voltage measured until a
repeatable value was obtained (Keithley 2400 Sourcemeter). The
conductivity of the printed layers was then calculated using finite-
size corrections.42 The measurements were made in-plane, both
parallel and perpendicular to the direction of the printed pattern.
The out-of-plane conductivity was not measured because even
though the CNC–PANI film forms crystals they are randomly
oriented in the film and homogenously distributed, giving rise
to direction independent conductivity. The difference in the
values presented in Table 3 stem from inhomogeneous printing.
The measurements were carried out under ambient conditions
with a relative humidity of 20.1% and at 24.7 1C.
3. Results and discussion
3.1 Characteristics of the inks
In order to prepare PANI in the form of highly conducting
nanoparticles, the well-established emulsion polymerization
Table 1 The composition of the CNC–PANI ink in comparison with the PANI ink and other experimental conditions used in the study
Ink
CNC–PANI
Solvent volume ratio CNC (0.1 wt%)/glycerol, 1 : 1
Wt ratio CNCdry/aniline 1 : 15
Concentration of aniline [M] 0.16
Concentration of APS [M] 0.08
Molar ratio APS/aniline 1:2
Concentration of DBSA [M] 0.19
Molar ratio aniline/APS/DBSA 1.0 : 0.5 : 1.2
J. Mater. Chem. C
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Journal of Materials Chemistry C
method using DBSA as dopant was used in this study.24,43,44
In this method aniline is polymerized in the micellar solution
of DBSA using APS as a chemical oxidant. Table 1 shows the
concentrations and molar ratios between aniline, APS and
DBSA used in this study. In Table 1 the volume ratio between
water and glycerol is also shown together with the used CNC
concentration. The volume ratio of 1 between water and glycerol
was found to be suitable for the polymerization of stable
suspensions of PANI. When the glycerol content was increased
a globular suspension was obtained.
The ratio between the molar concentration of aniline and
APS is crucial for successful formation of PANI in the conducting
emeraldine salt (ES) form. It has been found that an optimum
molar ratio of aniline to APS is 2.43 However, Moulton et al.24
found this ratio not suitable for the formation of conducting
PANI and used the molar ratio aniline/APS of 1 instead. The
reason for that might have been the use of a rather low concen-
tration of DBSA (the same as APS concentration), because at a low
DBSA concentration the polymerization time is increased. At too
high a DBSA concentration, on the other hand, the formed PANI
is not any more in the conducting form. It has been shown that
the DBSA concentration should be higher than the APS concen-
tration but not exceed the DBSA/APS molar ratio of 3.43 A
deficiency of oxidant concentration towards the monomer
concentration during polymerization has also been shown to
decrease the particle size of PANI.44
The morphology of the developed CNC–PANI and PANI inks
was characterized by TEM. Fig. 1a shows that the CNC crystals
itself have an elongated morphology with a width of approxi-
mately 10 nm and a length between 500 nm and 800 nm in
spite of their rather aggregated morphology. On the other hand,
the PANI in the PANI ink without CNC forms spherical particles
with a diameter of approximately 20 nm (Fig. 1b). The compo-
site particles of CNC and PANI in the CNC–PANI ink are shown
in Fig. 1c. In the composite, it can clearly be observed that the
PANI particles are colocalized with the CNC crystals over-dyeing
them making the CNC crystals not visible in the TEM image.
This is expected due to the negative charge of the –OSO3
surface groups of CNC and the positive charge of PANI in the
ES form.
UV-visible spectroscopy is a good method to characterize the
doping state in which PANI exists. It is generally agreed that
PANI exists in three forms depending on the extent of doping:
leucoemeraldine (fully reduced form), emeraldine (half-oxidized
form) and pernigraniline (fully oxidized form).45,46 The only
PANI
H2O/glycerol, 1 : 1
—
0.16
0.08
1:2
0.19
1.0 : 0.5 : 1.2
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Journal of Materials Chemistry C
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Fig. 1 Transmission electron micrographs of (a) the CNC crystals, (b) the
PANI nanoparticles and (c) the CNC–PANI ink.
electrically conducting form is the ES form which is obtained in
the presence of protons due to protonation of the basic sites in
PANI.45
The UV-visible spectra of the CNC–PANI and PANI inks
diluted with 0.01 M HCl are shown in Fig. 2. The p–p* band
appeared at around 355 nm and the band at 438 nm can be
assigned to the polaron band to p* band transition in both
spectra. The bands at 814 and 807 nm in the spectra of the
CNC–PANI and PANI inks, respectively, are assigned to the
transition between the p band and the polaron band.43 These
results confirm that the PANI in both inks is in its green
conducting ES form. The UV-visible absorption band for the
polaron transition of the ES form of PANI(DBSA) has been
reported to locate between 760 and 790 nm.24,42,43 That band
seems to shift to higher wavelengths when the conjugation
length in PANI increases.43 The polaron transition band of the
CNC–PANI ink is located at approximately 7 nm higher
wavelength than that of the PANI ink meaning that the
conjugation length in the CNC–PANI ink is a bit longer than
that in the PANI ink. Moreover, the disappearance of the so
called free-carrier tail in the near infrared region indicates a
coil-like conformation of PANI. This means that PANI is in a
twisted conformation where the polarons are isolated from
each other between the aromatic rings and therefore the
polaron band becomes rather narrow.25 The polaron band
in the CNC–PANI ink is also a bit broader than that in the
PANI ink meaning a more heterogeneous distribution of the
effective conjugation lengths.
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Fig. 2 UV-visible spectra of the CNC–PANI and PANI inks.
In order to judge if the prepared inks are suitable for
flexographic printing the rheological behavior of the developed
inks was studied. The results are shown in Fig. 3. The shear rate
was increased from 1 to 800 s 1 and then continuously
decreased back to 1 s 1. This shows that the flow is time-
dependent and thixotropic since the viscosity decreases with
time. The CNC–PANI ink displayed shear-thinning properties,
the dynamic viscosity decreased with increasing shear rate. The
viscosity of the PANI ink, on the other hand, showed only a
minor decrease at low shear rates and at higher shear rates of
410 s 1 the viscosity was almost constant close to a Newtonian
flow behaviour. In addition, at high shear rates (4200 s 1) the
viscosity of the CNC–PANI and PANI inks were comparable
with each other (Fig. 3). At lower shear rates, however, the
CNC–PANI ink shows a higher viscosity compared with the
PANI ink. CNC crystals colocalized with PANI nanoparticles
increases the viscosity of the ink as expected. The reason could
be the increased negative charge in the CNC–PANI ink due to
the charged CNC crystals increasing the inter-particle repulsion
and improving the dispersibility of the ink. Similar results
were obtained when the rheological properties of uncharged
formic acid hydrolyzed CNC were compared with the charged
TEMPO-oxidized CNC and sulfuric acid hydrolyzed CNC.37 The
viscosity of both inks can be considered to be suitable for the
Fig. 3 Rheological behavior of the CNC–PANI and PANI inks.
J. Mater. Chem. C

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flexographical printing method with the typical operation range
between 50 and 500 mPa s depending on the printed matter.47
3.2 Characteristics of the printed layers
The flexographic printing was performed by repeating the
printing procedure 1–10 times to investigate the surface cover-
age of the CNC–PANI and PANI inks on the MLCC paper
substrate. An optical microscope was used to estimate the
micro-scale distribution of printed material (Fig. 4) and AFM
was used to analyze the small-scale topography and roughness
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of printed layers (Fig. 5). Table 2 lists the roughness values of
the different samples.
Fig. 4a–d show the optical micrographs of 5 and 10 printed
layers of both inks (in Fig. 1-S, ESI† additionally graphs of 1 and
3 printed layers are shown) depicting the difference in the
effective coverage. The darker contrast in the micrographs
indicates a printed material with sufficient thickness and
density to change the optical contrast compared to the paper
Fig. 4 Optical micrographs of (a) 5 and (b) 10 layers of the CNC–PANI ink
and (c) 5 and (d) 10 layers of the PANI ink printed on MLCC paper and (e) a
photograph of the CNC–PANI print.
Fig. 5 5 mm  5 mm AFM images of (a) 5 (z-scale: 800 nm) and (b) 10
(z-scale: 600 nm) layers of CNC–PANI ink and (c) 5 and (d) 10 layers
(z-scale: 1000 nm) of the PANI ink printed on MLCC paper and (e) the bare
MLCC paper substrate (z-scale: 600 nm).
J. Mater. Chem. C
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Journal of Materials Chemistry C
Table 2 Root mean square roughness (Sq) and surface area ratio (Sdr)
values for different numbers of print layers of CNC–PANI and PANI ink on
MLCC paper
CNC–PANI ink PANI ink
Number Number
of layers Roughness of layers Roughness
1 Sq: 77.2 nm  10 nm 1 Sq: 118 nm  10 nm
Sdr: 44%  10% Sdr: 64%  10%
3 Sq: 115 nm  20 nm 3 Sq: 124 nm  15 nm
Sdr: 34%  8% Sdr: 52%  10%
5 Sq: 127 nm  17 nm 5 Sq: 181 nm  24 nm
Sdr: 20%  7% Sdr: 49%  8%
10 Sq: 107 nm  12 nm 10 Sq: 186 nm  20 nm
Sdr: 17%  5% Sdr: 59%  7%
substrate. However, AFM confirmed that thinner layers of the
material were also sporadically distributed in the interspaces.
For both inks, a full coverage of the darker contrast in micro-
graphs was achieved only after 10 print layers. However, the
contrast in micrographs was still somewhat heterogeneous,
suggesting variations in local thickness or density. The uneven
distribution is most probably due to the combination of the
roughness of the paper substrate and less than optimal ink
transfer and wettability due to the un-matching surface tension
of the ink and the surface chemistry and energy of the paper
substrate causing heterogeneity during ink spreading and
drying.30,31 On the other hand, a photograph of 10 layers of
the CNC–PANI ink printed on the MLCC paper (Fig. 4e) shows
that macroscopically a rather homogeneous layer was achieved
with 10 print layers (without the typical halo-effect of flexo-
graphic printing in the print borders).
The small-scale AFM topographs of the printed layers
captured from selected spots of the respective printed sample
are shown in Fig. 5 (additionally 1 and 3 printed layers are
shown in Fig. 2-S, ESI†). Some kaolin pigments (circled area)
are visible in the bare MLCC paper (Fig. 5e) but are covered by
the inks in the printed areas both after 5 and 10 print layers
(Fig. 5a–d). Visual characterization indicates that the printed
layers formed with the PANI ink show more continuous film-
like characteristics compared to the CNC–PANI layers with
more dispersed globular nanoscale features (average diameter
B200–400 nm). The dispersed nature of the surface is more
pronounced with 10 layers (Fig. 5b).
The mean square surface roughness (Sq) values show that
the small-scale surface roughness increased with the increasing
layer number of the PANI ink (Table 2). Increased roughness
also results in an increased surface area (Sdr). On the other
hand, the surface roughness of the CNC–PANI ink layers
remained quite comparable to the initial roughness of the
paper substrate (Sq: 102  15 nm, Sdr: 34  10%). In addition,
10 layers of the PANI ink showed a considerably higher rough-
ness than 10 layers of the CNC–PANI ink. The average effective
thickness of the printed layers was estimated from the local
difference between the mean plane value of the substrate and
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Journal of Materials Chemistry C
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Fig. 6 The relative surface coverage (---) and estimated thickness ( ) as
a function of the number of printed layers for CNC–PANI and PANI inks.
the average height value of the printed pattern in the AFM
image. The results are shown in Fig. 6. The deviations in the
estimated effective thickness values were generally large
(25–33%) due to the local heterogeneity of the MLCC paper
substrate and the ink layers. Therefore thicknesses higher than
500 nm can only be estimated with better reliability. For the
PANI ink, a relatively steep thickness increase is first observed
(up to 3 layers) after which the layer thickness does not change
significantly anymore. On the other hand, the CNC–PANI ink
shows a thickness increase only after three print layers.
Compared to the thickness, the relative surface coverage of
both inks, however, increases rather linearly with the increas-
ing number of printed layers (Fig. 6). However, the rate is faster
for the CNC–PANI ink compared to the PANI ink. Here it is
worth mentioning that the surface coverage determined from
optical micrographs did vary more in the lower coverage
samples (25% variation) but the coverage values were quite
repeatable in the higher ranges (10% variation). One reason
for the more efficient penetration of the CNC–PANI ink into the
paper substrate compared to the PANI ink could be a high
affinity of the cellulose-made CNC in the CNC–PANI ink to the
cellulose-based surface of the paper substrate.
CV is a widely used method for the characterization of
electrically conducting polymers and for studying their stability
and electroactivity.15 Fig. 7 shows the CVs measured from 5 and
10 layers of the CNC–PANI and PANI prints on the MLCC paper
in 0.1 M HCl electrolyte solution with the scan rate of
20 mV s 1. Due to the uneven coverage of both inks on the
paper substrate after only 1 or 3 printed layers continuous
conducting paths for electrons to move were not formed and
these films had negligible conductivity. For that reason the CV
characterization was conducted only with 5 and 10 layers.
Under acidic conditions at 0.4 V PANI is in its non-
conducting leucoemeraldine base form and transforms to the
conducting ES form upon oxidation of the film starting at
B0.1 V. On the reverse potential scan starting at 0.5 V the
PANI film reduces back to the leucoemeraldine base form. This
redox process is repeatable and stable over several potential
cycles for both prints. It can be seen from Fig. 7 firstly, that
higher currents are obtained for 10 printed layers compared to
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Fig. 7 Cyclic voltammograms of CNC–PANI and PANI prints with 5 and
10 printed layers in 0.1 M HCl, scan rate 20 mV s 1, the 5th scan is shown.
Inset: Oxidation peak current as a function of the square root of scan rate
for both inks.
5 printed layers for both inks and secondly, that the measured
oxidation and reduction currents are higher for the CNC–PANI
prints than for the PANI-prints. This means that PANI in the
prints made of the CNC containing ink has a higher electro-
activity than it has in the ink without CNC. The inset in Fig. 7
shows a rather linear relationship between the oxidation peak
current and the square root of the scan rate for both prints.
This confirms that the p-doping reaction of PANI in both prints
is controlled by the rate of diffusion of ions in the electrolyte
solution toward the electrode surface which is a typical beha-
vior for ECP films.
Finally, the effective electrical conductivity (s) of the prints
was examined using the 4-point probe method. Due to the
inhomogeneous surface structure of the printed layers s was
measured both parallel and perpendicular to the direction of
the printed pattern. The s values were calculated using the
estimated thicknesses found by the AFM measurements. The
electrical resistivity (r) and s for 5 and 10 printed layers of
CNC–PANI and PANI inks on MLCC paper substrate are shown
in Table 3. Due to the negligible conductivity of the unevenly
coated PANI films with only 1 or 3 printed layers those results
are not shown in Table 3. First of all, the s parallel to the
printed pattern was always higher than that measured
perpendicular to the pattern which was also expected. Secondly,
the s of the print after printing only 5 layers of the CNC–PANI
ink was rather low (B1.1  10 3 S cm 1). The corresponding
print made with the PANI ink, on the other hand, had
s = 2.2–6.7 S cm 1. It has been shown experimentally and by
computer simulations that if a conductive ink is enabled to
penetrate and absorb into the structure of the substrate the
continuous conductive path for electrons to travel is destroyed.8
This phenomenon may explain the lower s of the print made by
the CNC–PANI ink after 5 printed layers compared to the print
made by the PANI ink which does not penetrate into the
channels of the substrate as efficiently. Thirdly, the s of the
print after printing 10 layers of the CNC–PANI ink was as high
as B60 S cm 1, which is already higher than that of amorphous
J. Mater. Chem. C

Paper
Table 3 The electrical resistivity (r) and conductivity (s) values for 5 and 10 layers of CNC–PANI and PANI inks on MLCC paper measured parallel and
perpendicular to the printed pattern
5 Layers
1
r [O m] s [S cm ]
Ink 8 > 8 >
CNC–PANI — 7.14–12.8 — 0.0011–0.0014
PANI 0.0014–0.0026 0.0025–0.0045 3.7–6.7 2.2–3.9
carbon. Corresponding prints made of the PANI ink had
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s = 0.8–1.7 S cm 1. The considerable difference in the con-
ductivity of the CNC–PANI film and the PANI film with 10 print
layers could reflect that a more continuous and sufficiently
homogeneous film has been formed on the surface with
CNC–PANI ink. This is supported by the lower roughness of
the CNC–PANI layer, which is known to lead to lower resistance.
In addition to the topographical considerations, surface chem-
istry has been shown to have a role in the electrical perfor-
mance of ECPs. Previously, dedoping of acidic conducting
polymers by a more basic nature of the paper substrate has
been reported.48 The CNC matrix could stabilize doped PANI on
the MLCC substrate.
PANI synthesized by the emulsion polymerization method
using DBSA as dopant has shown conductivities of s = 15 
3 S cm 1 measured on a pellet.24 Ink-jet printed PANI(DBSA)
synthesized using the same molar ratio of aniline/APS/DBSA
(1 : 0.5 : 1.2) as in this study had conductivities of s = 4.3 
0.6  10 3 S cm 1.44 Solution cast films of nanocomposites of
CNF and PANI doped with HCl or p-toluenesulfonic acid had s
= 10 2 S cm 1 20 and in another study with 30 wt% loading of
PANI s = 4.3  10 2 S cm 1.22 Vacuum filtrated CNF/PANI
composites with 50 wt% loading of PANI showed s = 1.7 
10 1 S cm 1.21 It is possible to prepare PANI with a high s in a
colloidal dispersion mode using stabilizers such as poly-
N-vinylpyrrolidone, sodium dodecylsulfate, Tween 20 and
Pluronic F108. PANI films synthesized in presence of these
stabilizers have shown conductivities as high as 18.4  0.02,
30.40  0.08, 8.39  0.04 and 25.9  0.01 S cm 1, respectively.26
The electroactivity of the prints investigated by the CV measure-
ments in this study was also higher for the prints made with the
CNC containing ink than with the ink without CNC corres-
ponding well with the results of the conductivity measure-
ments. It is, however, surprising why the s of the print made
with the CNC containing ink was that high and why it was that
much higher than the s of the print made with the ink without
CNC. Tkalya et al.49 and Mendez et al.50 have shown that the
electrical percolation threshold with respect to the conducting
polymer can be lowered significantly in composites of PEDOT/
PSS and cellulose nanowhiskers blended with polystyrene (PS).
The cellulose nanowhiskers act as a percolating scaffold for the
conducting polymer which adsorbs on the cellulose surface
forming a conducting network. Aligned multi-walled carbon
nanotubes (MWCNTs) compared with highly entangled and
agglomerated MWCNTs dispersed in a PS matrix show also a
much lower percolation threshold.51 In our case a similar
J. Mater. Chem. C
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Journal of Materials Chemistry C
10 Layers
r [O m] s [S cm 1]
8 > 8 >
0.00015–0.00028 0.00016–0.00031 35.7–66.3 32.6–60.7
0.0058–0.0096 0.0013–0.078 1.04–1.70 0.77–1.29
phenomenon could be the reason for the higher s found in
the prints made with the CNC containing ink. The CNC
crystals with a negative charge form a platform and serve as
counterions for some part of the synthesized PANI which are
surrounded by the PANI(DBSA) nanospheres. In the ink with-
out CNC only the PANI(DBSA) nanospheres form the conduct-
ing network where the nanospheres are obviously not as well
dispersed as in the presence of CNC and the conducting
network is therefore shorter. Koga et al. have provided highly
conductive and printable composites of CNTs using anionic
CNF as a nanodispersing agent.11 They found a deviation
between the experimental and theoretically predicted s when
the CNT volume fraction of 0.048 was exceeded. After that
point the experimental s values were higher than the theore-
tical values. This was explained to be a result of the ionic
conduction phenomenon caused by a large amount of ionic
–COONa groups on the surface of CNF. Also, in our case some
part of the conductivity in the CNC–PANI prints could be ionic
conduction due to the sulfate half-esters (–OSO3 ) formed on
the surface of the crystals during the sulfuric acid hydrolysis
of cellulose.
4. Conclusions
This study evaluates the benefits of using CNC as a nanodis-
persing agent and glycerol as a viscosity modifier in the PANI
containing conductive ink. The ordered nano-sized crystal
structure and high surface charge made CNC a suitable
additive for the ink formulation of the spherical nanoparticles
of PANI(DBSA). The CNC–PANI ink was found to be suitable
for flexographical printing and the PANI(DBSA) in the prints
showed high electroactivity and stability. A stable nanoparti-
culate CNC–PANI ink was obtained with the high electrical
conductivity of the printed films with ten layers being more
than an order of magnitude higher than that for the corres-
ponding film without CNC. Suitable application areas for this
kind of a CNC–PANI print could be its use e.g. as a strain
sensor or as a bioactuator, in a drug delivery device or as
electronic paper in which the biocompatible nature of the
print would be beneficial.
Conflicts of interest
There are no conflicts to declare.
This journal is © The Royal Society of Chemistry 2017

Journal of Materials Chemistry C
Acknowledgements
The authors wish to express their appreciation to Dr Markus
Peurla and MSc Peter Kunnas for performing the TEM
measurements.
Notes and references
1 A. Kamyshny and S. Magdassi, Conductive Nanomaterials
for Printed Electronics, Small, 2014, 10, 3515.
2 S. Park, M. Vosguerichian and Z. Bao, A Review of Fabrica-
Published on 03 November 2017. Downloaded by RSC Internal on 21/11/2017 11:16:01.
tion and Application of Carbon Nanotube Film-Based Flex-
ible Electronics, Nanoscale, 2013, 5, 1727.
3 F. Hoeng, A. Denneulin and J. Bras, Use of Nanocellulose in
Printed Electronics: a Review, Nanoscale, 2016, 8, 13131.
4 N. L. Vaklev, R. Müller, B. V. O. Muir, D. T. James, R. Pretot,
P. Van der Schaaf, J. Genoe, J.-S. Kim, J. H. G. Steinke and
A. J. Campbell, High-Performance Flexible Bottom-Gate,
Organic Field-Effect Transistors with Gravure Printed Thin
Organic Dielectric, Adv. Mater. Interfaces, 2014, 1, 13000123.
5 E. M. Hamad, S. E. R. Bilatto, N. Y. Adly, D. S. Correa,
B. Wolfrum, M. J. Schöning, A. Offenhäusser and
A. Yakushenko, Inkjet Printing of UV-Curable Adhesive
and Dielectric Inks for Microfluidic Devices, Lab Chip,
2016, 16, 70.
6 D. Tobjörk, H. Aarnio, P. Pulkkinen, R. Bollström,
A. Määttänen, P. Ihalainen, T. Mäkelä, J. Peltonen,
M. Toivakka, H. Tenhu and R. Österbacka, IR-Sintering of
Ink-Jet Printed Metal-Nanoparticles on Paper, Thin Solid
Films, 2012, 520, 2949.
7 G. Chinga-Carrasco, D. Tobjörn and R. Österbacka, Inkjet-
Printed Silver Nanoparticles on Nano-Engineered Cellulose
Films for Electrically Conducting Structures and Organic
Transistors: Concept and Challenges, J. Nanopart. Res.,
2012, 14, 1213.
8 A. Penttilä, J. Sievänen, K. Torvinen, K. Ojanperä and
J. A. Ketoja, Filler-Nanocellulose Substrate for Printed Elec-
tronics: Experiments and Model Approach to Structure and
Conductivity, Cellulose, 2013, 20, 1413.
9 F. Hoeng, J. Bras, E. Gicquel, G. Krosnicki and A. Denneulin,
Inkjet Printing of Nanocellulose-Silver Ink onto Nanocellu-
lose Coated Cardboard, RSC Adv., 2017, 7, 15372.
10 A. Tang, Y. Liu, Q. Wang, R. Chen, W. Liu and Z. Fang,
A New Photoelectric Ink Based on Nanocellulose/CdS Quan-
tum Dots for Screen-Printing, Carbohydr. Polym., 2016,
148, 29.
11 H. Koga, T. Saito, T. Kitaoka, M. Nogi, K. Suganuma and
A. Isogai, Transparent, Conductive, and Printable Compo-
sites Consisting of TEMPO-Oxidized Nanocellulose and
Carbon Nanotubes, Biomacromolecules, 2013, 14, 1160.
12 Y. Habibi, L. A. Lucia and O. J. Rojas, Cellulose Nanocrystals:
Chemistry, Self-Assembly, and Applications, Chem. Rev.,
2010, 110, 3479.
13 J. A. Shatkin, T. H. Wegner, E. M. Bilek and J. Cowie, Market
Projections of Cellulose Nanomaterial-Enabled Products
Part. 1: Applications, Tappi J., 2014, 13, 9.
This journal is © The Royal Society of Chemistry 2017
View Article Online
Paper
14 A. G. MacDiarmid, ’’Synthetic Metals’’: A Novel Role for
Organic Polymers (Nobel Lecture), Angew. Chem., Int. Ed.,
2001, 40, 2581.
15 J. Kankare, Electronically Conducting Polymers: Basic Meth-
ods of Synthesis and Characterization, in Electrical and Optical
Polymer Systems, ed. Wise, D. L., Wnek, G. E., Trantolo, D. J.,
Cooper, T. M. and Gresser, J. D., Marcel Dekker, Inc., New
York, 1998, 6, 167–199.
16 A. G. MacDiarmid, Polyaniline and Polypyrrole: Where Are
We Headed?, Synth. Met., 1997, 84, 27.
17 L. H. C. Mattoso, E. S. Medeiros, D. S. Baker, J. Avloni,
D. F. Wood and W. J. Orts, Electrically Conductive Nano-
composites made from Cellulose Nanofibrils and Polyani-
line, J. Nanosci. Nanotechnol., 2009, 9, 2917.
18 S. Bocchini, A. Chiolerio, S. Porro, D. Accardo, N. Garino,
K. Bejtka, D. Perrone and C. F. Pirri, Synthesis of
Polyaniline-Based Inks, Doping Thereof and Test Device
Printing Towards Electronic Applications, J. Mater. Chem.
C, 2013, 1, 5101.
19 A. Chiolerio, S. Bocchini and S. Porro, Inkjet Printed Nega-
tive Supercapacitors: Synthesis of Polyaniline-Based Inks,
Doping Agent Effect, and Advanced Electronic Devices
Applications, Adv. Funct. Mater., 2014, 24, 3375.
20 A. Chiolerio, S. Bocchini, M. Crepaldi, K. Bejtka and
C. F. Pirri, Bridging Electrochemical and Electron Devices:
Fast Resistive Switching Based on Polyaniline from One Pot
Synthesis Using FeCl3 as Oxidant and Co-Doping Agent,
Synth. Met., 2017, 229, 72.
21 N. D. Luong, J. T. Korhonen, A. J. Soininen, J. Ruokolainen,
L.-S. Johansson and J. Seppälä, Processable Polyaniline
Suspensions Through in Situ Polymerization onto Nano-
cellulose, Eur. Polym. J., 2013, 49, 335.
22 W. He, J. Tian, H. Jin and Y. Li, Characterization and
Properties of Cellulose Nanofiber/Polyaniline Film Compo-
sites Synthesized through in Situ Polymerization, Bio-
Resources, 2016, 11, 8535.
23 A. Riede, M. Helmstedt, I. Sapurina and J. Stejskal, In Situ
Polymerized Polyaniline Films. 4. Film Formation in Dis-
persion Polymerization of Aniline, J. Colloid Interface Sci.,
2002, 248, 413.
24 S. E. Moulton, P. C. Innis, L. A. P. Kane-Maguire, O. Ngamna
and G. G. Wallace, Polymerization and Characterization of
Conducting Polyaniline Nanoparticle Dispersions, Curr.
Appl. Phys., 2004, 4, 402.
25 Y. Xia, J. M. Wiesinger and A. G. MacDiarmid, Camphor-
sulfonic Acid Fully Doped Polyaniline Emeraldine Salt:
Conformations in Different Solvents Studied by an Ultravio-
let/Visible/Near-Infrared Spectroscopic Method, Chem.
Mater., 1995, 7, 443.
26 V. Kašpárková, P. Humpilı́ček, Z. Capáková, P. Bober,
J. Stejskal, M. Trchová, P. Rejmontová, I. Junkar,
M. Lehocký and M. Mozetič, Cell-Compatible Conducting
Polyaniline Films Prepared in Colloidal Dispersion Mode,
Colloids Surf., B, 2017, 157, 309.
27 N. Kim, S. Kee, S. H. Lee, B. H. Lee, Y. H. Kahng, Y.-R. Jo,
B.-J. Kim and K. Lee, Highle Conductive PEDOT:PSS
J. Mater. Chem. C

Paper
Nanofubrils Induced by Solution-Processed Crystallization,
Adv. Mater., 2014, 26, 2268.
28 X. Fan, B. Xu, S. Liu, C. Cui, J. Wang and F. Yan, Transfer-
Printed PEDOT:PSS Electrodes Using Mild Acids for High
Conductivity and Improved Stability with Application to
Flexible Organic Solar Cells, ACS Appl. Mater. Interfaces,
2016, 8, 14029.
29 J. Sarfraz, P. Ihalainen, A. Määttänen, J. Peltonen and
M. Lindén, Printed hydrogen sulfide gas sensor on paper
substrate based on polyaniline composite, Thin Solid Films,
2013, 534, 621.
Published on 03 November 2017. Downloaded by RSC Internal on 21/11/2017 11:16:01.
30 P. Ihalainen, A. Määttänen, J. Järnström, D. Tobjörk,
R. Österbacka and J. Peltonen, Influence of Surface Proper-
ties of Coated Papers on Printed Electronics Res., Ind. Eng.
Chem., 2012, 51, 6025.
31 J. Sarfraz, P. Ihalainen, A. Määttänen, R. Bollström,
T. Gulin-Sarfraz, J. Peltonen and M. Lindén, Stable ink
dispersions suitable for roll-to-roll printing with sensitivity
towards hydrogen sulphide gas, Colloids Surf., A, 2014,
460, 401.
32 H. Kipphan, Handbook of Print Media, Springer, Heidelberg,
2001.
33 S. Zhang, P. Kumar, A. S. Nouas, L. Fontaine, H. Tang and
F. Cicoira, Solvent-Induced Changes in PEDOT:PSS Films
for Organic Electrochemical Transistors, APL Mater., 2015,
3, 014911.
34 F. Ghamouss, A. Brugère, A. C. Anbalagan, B. Schmaltz,
E. Luais and F. Tran-Van, Novel glycerol Assisted Synthesis
of Polypyrrole Nanospheres and Its Electrochemical Proper-
ties, Synth. Met., 2013, 168, 9.
35 M.-W. Lee, M.-Y. Lee, J.-C. Choi, J.-S. Park and C.-K. Song,
Fine Patterning of Glycerol-Doped PEDOT:PSS on Hydro-
phobic PVP Dielectric with Ink Jet for Source and Drain
Electrode of OTFTs, Org. Electron., 2010, 11, 854.
36 S. H. Eom, S. Senthilarasu, P. Uthirakumar, S. C. Yoon,
J. Lim, C. Lee, H. S. Lim, J. Lee and S.-H. Lee, Polymer Solar
Cells Based on Inkjet-Printed PEDOT:PSS Layer, Org. Elec-
tron., 2009, 10, 536.
37 D. Klemm, F. Kramer, S. Moritz, T. Lindström,
M. Ankerfors, D. Gray and A. Dorris, Nanocelluloses: A
new family of nature-based materials, Angew. Chem., Int.
Ed., 2011, 50, 5438.
38 W. Xu, H. Grénman, J. Liu, D. Kronlund, B. Li, P. Backman
and C. Xu, Mild Oxalic-Acid-Catalyzed Hydrolysis as a Novel
J. Mater. Chem. C
View publication stats
View Article Online
Journal of Materials Chemistry C
Approach to Prepare Cellulose Nanocrystals, ChemNanoMat,
2017, 3, 109.
39 J. Sarfraz, A. Määttänen, P. Ihalainen, M. Keppeler,
M. Lindén and J. Peltonen, Printed Copper Acetate Based
H2S Sensor on Paper Substrate, Sens. Actuators, B, 2012,
173, 868.
40 R. Bollström, A. Määttänen, D. Tobjörk, P. Ihalainen,
N. Kaihovirta, R. Österbacka, J. Peltonen and M. Toivakka,
A multilayer coated fiber-based substrate suitable for
printed functionality, Org. Electron., 2009, 10, 1020.
41 A. Määttänen, U. Vanamo, P. Ihalainen, P. Pulkkinen,
H. Tenhu, J. Bobacka and J. Peltonen, A low-cost paper-
based inkjet-printed platform for electrochemical analyses,
Sens. Actuators, B, 2013, 177, 153.
42 F. M. Smits, Measurement of sheet resistivities with the
four-point probe, Bell Syst. Technical Journal, 1958, 37, 711.
43 M. G. Han, S. K. Cho, S. G. Oh and S. S. Im, Preparation and
Characterization of Polyaniline Nanoparticles Synthesized
from DBSA Micellar Solution, Synth. Met., 2002, 126, 53.
44 O. Ngamna, A. Morrin, A. J. Killard, S. E. Moulton,
M. R. Smyth and G. G. Wallace, Inkjet Printable Polyaniline
Nanoformulations, Langmuir, 2007, 23, 8569.
45 W. S. Huang, B. D. Humprey and A. G. MacDiarmid,
J. Chem. Soc., Faraday Trans., 1986, 82, 2385.
46 S. Quillard, K. Berrada, G. Louarn, S. Lefrant, A. Lapkowski
and A. Prón, New J. Chem., 1995, 19, 365.
47 K. Suganuma, SpringerBriefs in Electrical and Computer
Engineering, Introduction to Printed Electronics, 2014, vol.
74, p. 1.
48 B. Trnovec, M. Stanel, U. Hahn, A. C. Hübler, H. Kempa,
R. Sangl and M. Forster, Coated Paper for Printed Electro-
nics, Prof. Papermaking, 2009, 6, 48.
49 E. Tkalya, M. Ghislandi, W. Thielemans, P. van der Schoot,
G. de With and C. Koning, Cellulose Nanowhiskers Tem-
plating in Conductive Polymer Nanocomposites Reduces
Electrical Percolation Threshold 5-fold, ACS Macro Lett.,
2013, 2, 157.
50 J. D. Mendez and C. Weder, Synthesis, Electrical Properties,
and Nanocomposites of Poly(3,4-ethylenedioxythiophene)
Nanorods, Polym. Chem., 2010, 1, 1237.
51 N. Grossiord, J. Loos, L. van Laake, M. Maugey, C. Zakri and
C. E. Koning, High-Conductivity Polymer Nanocomposites
Obtained by Tailoring the Characteristics of Carbon Nano-
tube Fillers, Adv. Funct. Mater., 2008, 18, 3226.
This journal is © The Royal Society of Chemistry 2017