Sensors & Actuators: B.

Chemical xxx (xxxx) xxx-xxx

Contents lists available at ScienceDirect

Sensors & Actuators: B. Chemical

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Functional aqueous-based polyaniline inkjet inks for fully printed high-performance
pH-sensitive electrodes
Emanuel Bilbao a, b, c, Sunil Kapadia d, Verónica Riechert e, f, Javier Amalvy e, f, Fabricio N. Molinari g,

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Mariano M. Escobar b, c, g, Reinhard R. Baumann d, Leandro N. Monsalve a, b, ⁎
a
Departamento de Nanomateriales funcionales, INTI Micro y Nanotecnologías, Av. Gral. Paz 5445 (B1650WAB) San Martín, Buenos Aires, Argentina
b
Consejo Nacional de Investigaciones Científicas y Técnicas, Godoy Cruz 2290 (C1425FQB) CABA, Argentina
c
Universidad Nacional del Oeste, Gral. Manuel Belgrano 369 (B1718) San Antonio de Padua, Buenos Aires, Argentina
d
Department of Digital Printing and Imaging Technology, Technische Universität Chemnitz, Reichenhainer Str. 70 09126, Chemnitz, Germany
e
Grupo (Nano)Materiales Poliméricos, INIFTA, Diagonal 113, Casco Urbano (B1900) La Plata, Buenos Aires, Argentina
f
Centro de Investigación y Desarrollo en Ciencia y Tecnología de Materiales (CITEMA), Universidad Tecnológica Nacional (UTN) - Comisión de Investigaciones Científicas de la Provincia de Buenos

D
Aires (CIC), Av. 60 y 124, (1923) Berisso, Buenos Aires, Argentina
g
INTI Materiales Avanzados, Av. Gral. Paz 5445 (B1650WAB) San Martín, Buenos Aires, Argentina
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ARTICLE INFO ABSTRACT

Keywords: pH sensors are extremely useful in various applications such as health, food and environmental monitoring. Due
Conductive ink to this fact the development of planar, low-cost and high-performance pH sensors that can be fabricated in large
Aqueous-based ink scale are highly appreciated. In this work we fabricated a polyaniline-based potentiometric pH sensor using two
Potentiometric electrode printing techniques. The working electrode was fabricated by printing a carbon ink layer onto Valox® by screen
Printed electronics
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printing and subsequently modifying its active area by printing with a polyaniline ink by inkjet printing. Dif-
ferent water-based formulations of the polyaniline ink using acrylic dispersions as binders were tested in order
to optimize printability, adhesion, rub resistance and functionality of the printed electrodes. These electrodes
showed an outstanding sensitivity (up to 69.1 mV/pH), slightly higher than polyaniline electrodes fabricated by
electropolymerization onto carbon paste electrodes and also comparable to glass electrodes. Moreover, their re-
sponse to synthetic sweat was analyzed, demonstrating that there are suitable for application in wearable tech-
nology.
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1. Introduction conducting polymer have been developed: batteries, sensors, actuators,

electromagnetic shielding, antistatic coatings, corrosion protection, and
pH measurements are highly relevant in many fields such as clini- electro-optic and electrochromic devices [11].
cal analysis, environmental monitoring and food industry. Particularly, The synthesis of PANI, either chemical or electrochemical, yields
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pH measurements can be used for the analysis of parameters of clinical
relevance including glucose [1–3], triglycerides [4] and wound healing
monitoring [5–7]. Moreover, pH of skin can be a useful physiological
parameter for preventing dehydration during exercise and skin disor-
ders [8–10]. For these reasons, the development of small and low-cost
pH sensors that could be fabricated at large scale (i.e.: by printing tech-
niques) are highly desirable.
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particles that are insoluble in most solvents. Therefore, the efforts for
enh6ancing its processability are focused on controlling particle size and
dispersability. For instance, it is possible to obtain well dispersed PANI
nanofibers in acidic medium by performing the polymerization reaction
in solution at 60 °C [12], or nanospheres if the reaction is carried away
in emulsion [13]. These nanoparticles were successfully used for the
preparation of inkjet inks for printing ammonia sensors [14], superca-

Polyaniline (PANI) is a conducting polymer, which can be obtained pacitors [15] and to functionalize electrodes for biosensing [16]. Due to
by oxidative polymerization of aniline. PANI is well-known for its ease its ability of being doped by acids, its conduction properties and charge
of synthesis, environmental stability, and unique acid/base doping/de- density are affected by pH [17] and thus it can be employed for the fab-
doping and oxidation/reduction chemistry. Many applications for this rication of active layers for pH sensing.

⁎ Corresponding autor at: Departamento de Nanomateriales funcionales, INTI Micro y Nanotecnologías, Av. Gral. Paz 5445 (B1650WAB) San Martín, Buenos Aires, Argentina.
Email address: monsalve@inti.gob.ar (L.N. Monsalve)

https://doi.org/10.1016/j.snb.2021.130558
Received 16 March 2021; Received in revised form 29 June 2021; Accepted 2 August 2021
Available online xxx
0925-4005/ © 2021.
E. Bilbao et al.
Regarding application of PANI in the fabrication of pH sensors, it has
been reported several years ago. A study on the behavior of PANI-coated
glassy carbon electrodes as potentiometric pH sensor was described by
Karyakin et al., who found that the potential vs. pH slope varied from
118 mV at pH < 3–70 mV at pH > 5 [1]. Moreover, the same authors
found later that the sensitivity could be further improved to 90 mV up
to pH 8 by dissolving PANI with camphorsulfonic acid in chloroform
and using the solution for coating glassy carbon electrodes by drop cast-
ing [2]. Since then, the fabrication and characterization of pH sensing
devices based either on conductivity [18] or potential [6,7] have been
developed. However, PANI-based potentiometric pH sensing electrodes
fabricated onto flexible substrates using carbon inks as conductive layer
material presented diminished sensitivity below 60 mV/pH. This could
be due to the presence of interferences that contribute to the redox po-
tential at the active layer.
PANI layers can be deposited by inkjet printing, which is a fast, re-
producible and scalable method for depositing functional patterns, by
three different approaches: a) printing of monomer and polymerization
once printed [19,20], b) dissolution of PANI in organic solvents [21,22]
and c) dispersion of PANI nanoparticles in aqueous media [3,23,24].
Aqueous-based inks are the most desirable due to their safety and low
environmental impact. However, special care must be taken for ensuring
printability and mechanical stability of the PANI layer in any case. For
this, the particle size and concentration must be controlled and other
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non-volatile additives such as film-forming resins and stabilizers must
be added for dispersion.
Acrylic resins are a group of thermoplastic substances derived from
acrylic acid, methacrylic acid, and other related compounds. More
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specifically, water-based acrylic dispersions are used in its dispersed
form for textile finishes, adhesives, lacquer, and printing inks. They pro-
vide adhesion and mechanical stability to the printed layer. Moreover,
they are safer and more environmentally friendly than solvent-based
formulations. However, most commercial acrylic dispersion formula-
tions developed for inkjet printing inks are slightly alkaline, which
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make them unsuitable for formulations containing conductive polymers
such as polyaniline (PANI) [25]. Moreover, the colloidal stability of
both acrylic latex nanoparticles and conductive polymer nanoparticles is
compromised. To overcome this problem, custom-made acrylic binders
must be formulated. For instance, Wang et al. prepared an hydrogel
made of PANI, polyacrylic acid and phytic acid that presented improved
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adhesion onto silicon-based anodes in lithium-ion batteries [26].
For the fabrication of pH-sensitive electrodes using printing tech-
niques, electrodeposition of the active layer onto conductive printed
electrodes is the most common method so far. Electrodeposition ensures
layer homogeneity, purity and mechanical stability of the active layer.
However, little is known about the sensing properties of printed pH-sen-
sitive electrodes with electrodeposited active layer compared to printed
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active layer.
The present work addresses the fabrication of fully printed pH-sen-
sitive electrodes based on aqueous PANI inks on a Valox® flexible sub-
strate. The PANI inks were prepared from chemically synthesized PANI
nanofibers and the effect of the addition of different acrylic dispersions
was evaluated. The electrodes comprised a screen-printed carbon elec-
trode of 1 mm diameter modified by inkjet-printing of a layer of PANI
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on top. Moreover, screen-printed carbon electrodes modified with PANI
by electropolymerization were made for comparing their pH sensing
properties. The printability of the PANI inks, the mechanical properties
of the PANI layer and the performance of the electrodes for pH sensing
were also investigated.
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Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
2. Experimental
2.1. General remarks
Aniline (Anedra, Argentina) was double distilled before use. The fol-
lowing reagents were ACS grade and used without further purification.
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Hydrochloric acid and lithium chloride were acquired from Anedra (Ar-
gentina). Potassium persulphate (K2S2O8 KPS), sodium dodecyl sulfate
(CH3(CH2)11SO4Na SDS), potassium biphthalate (HOOCC6H4COOK), bo-
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rax (Na2B4O7·10H2O), potassium dihydrogen phosphate (KH2PO4), dis-
odium hydrogen phosphate (Na2HPO4), sodium chloride (NaCl), potas-
sium chloride (KCl), magnesium chloride hexahydrate (MgCl2·6H2O),
calcium chloride (CaCl2), and sodium hydroxide (NaOH) were pur-
chased from Biopack (Argentina). Buffer solutions of pH 4.01, 7 and
10 (20 °C) traceable to SRM from NIST and PTB were purchased from
Merck. Ethyl acrylate (CH2 = CHCOOC2H5, EA) from Fluka, methyl
methacrylate (CH2 = C(CH3)COOCH3, MMA) and methacrylic acid
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(CH2 = C(CH3)COOH, MAA) from Sigma Aldrich, and ethylene gly-
col dimethacrylate (CH2 = C(CH3)COOCH2CH2OCOC(CH3) = CH2,
EGDMA) from Merck.
2.2. Ink formulation
A suspension containing 4 mg mL−1 of PANI nanofibers was synthe-
sized according to the method described by Kaner [12] (see supplemen-
tary material for details). The suspension was stabilized with 8 mg mL−1
of SDS, and this suspension was nominated PANI-0.
Three waterborne acrylic resins were obtained by semicontinuous
emulsion polymerization. Resins contain mainly EA and MMA in dif-
ferent ratios, achieving up to 98 wt.% of total monomer content. As
EA/MMA mass ratio increase, glass transition temperature of resin de-
crease. Additionally, they contain up to 3 wt.% of MAA and ∼0.1 wt.%
of EGDMA (Table S1). Increasing MAA content, pH of the final disper-
sion goes down and the amount of −COOH increases, expecting a bet-
ter adhesion to the substrate. On the other hand, EGDMA acts as poly-
mers crosslinker to improve mechanical properties. The initial charge of
monomers in reactor is defined based on the desired EA/MMA ratio in
the resin, taking into account the reactivity ratio of monomers [27]. In
all synthesis, reactor is initially charged with all EA (monomer with less
reactivity), a fraction of MMA and EGDMA, emulsifier (SDS) and dis-
tilled water (Table S2).
The dispersion was stirred at 270 rpm during 30 min, while it is
heated to 60 °C with nitrogen gas passing through the bulk to elimi-
nate dissolved oxygen. After that, the initiator (KPS) dissolved in a small
amount of water was added to the reactor and, after 15 min of reac-
tion, a monomer feed was added to the reactor at 2 g/min. The feed is
an emulsion previously prepared dispersing the rest of monomers (part
of MMA and EGDMA, and all MAA), emulsifier (SDS) and distilled wa-
ter and emulsified at 2000 rpm during 45 min. Then, nitrogen flow was
bubbled into the emulsion during 30 min. Once all feed was added, tem-
perature was raised to 80 °C and reaction occured by 2 h. The resulting
resins were named R1, R2 and R3, and their corresponding glass transi-
tion temperatures were -0.6, -0.2 and -7.2 °C as determined by DSC.
In order to formulate the inks, acrylic lattices were added into an
aliquot of PANI-0 to fulfill a weight ratio PANI:resin of 1:1 on dry basis,
resulting in inks PANI-R1, PANI-R2 and PANI-R3, with a solids content
of 16 mg mL−1.
The surface tension was measured by the Du Noüy method with a
Attension Sigma 700 force tensiometer. Viscosity was measured with a
rotatory viscometer Myr VR 3000 series, at 264 s−1 shear rate.
E. Bilbao et al. Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx

2.3. Device fabrication 2.6. Adhesion resistance

A screen printed three-electrode cell array was used, with a working Adherence tests were performed by taping an adhesive tape brand
electrode and a counter electrode of carbon paste. A reference electrode Scotch (3 M, Argentina) with a pressure of 10 N cm−1 on the sensors, re-
was printed using a commercial carbon and silver chloride paste onto moving the tape, and scanning the material removed by the tape with
Valox® substrates according to previously reported [28]. For the fabri- a desktop scanner. A relative adherence strength was determined by

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cation of electrodes with electropolymerized PANI (PANI-EQ), a 10 μL graphical analysis using software ImageJ [30]. Detailed experimental
drop of solution containing 0.5 M aniline and 1 M HCl was placed on information and results are also presented in section 3.1 of the supple-
the electrodes, and then, 25 sinusoidal potential cycles between -0.2 mentary information.

and +1.0 V vs the screen-printed reference electrode (SPRE) were per-
formed at 100 mV s−1 (the working electrode was cleaned previously cy-
cling potential 10 times in HCl 1 M between -0.3 V and 1.1 V at 100 mV
s−1) [7]. For the fabrication of fully printed electrodes, five layers of
PANI inks were printed on top of the working electrodes with 2540 dpi
resolution with a Dimatix 2850 Materials Printer (Fujifilm, USA) using
DMC 11,610 cartridges. Each cartridge has a reservoir of capacity of
1.5 mL and a piezoelectric printhead with 16 nozzles linearly spaced
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3. Results and discussion
3.1. Ink formulation and characterization
All PANI inks were formulated from a stable aqueous dispersion of
PANI nanofibers. However, this dispersion was not suitable for inkjet
printing since printheads tended to clog with this dispersion and the

at 254 microns with typical drop volume of 10 picoliters. Considering
this nominal volume of the drop, the printing resolution and the area of
the working electrode printed with PANI inks (a circle of 1 mm diame-
ter = 0.79mm2), about 0.079 microliters of ink are consumed for print-
ing each layer on an individual electrode. Pictures of a fully printed elec-
trode and an electrode fabricated by electropolymerization are shown in
Fig. 1a and b respectively.
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layers of deposited PANI showed poor adhesion and homogeneity. The
addition of SDS to the aqueous dispersion for inkjet printing seemed
to be a useful strategy because it stabilizes the dispersion and reduces
its surface tension. Moreover, it has been successfully used in previous
works for the formulation of inkjet inks from aqueous-based dispersions
[3,23,24]. For this reason, we added 8 mg/mL of SDS to the PANI aque-
ous dispersion to improve printability. Moreover, since the PANI layer

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2.4. Electrochemical characterization
Potentiometric measurements were performed with a potentiostat
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Teq4 (Nanotec, Argentina) by measuring the open circuit potential be-
tween the working electrode and a saturated calomel electrode (SCE)
as reference electrode (input impedance > 1012 ohm). A more detailed
description of the measuring configuration is presented in sections 4.1
and 4.2 of the supplementary information. The pH of the test solutions
was measured with a Sanxin MP512 pH meter equipped with a glass
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on the pH electrodes is exposed, it should present good adhesion to
the plastic substrate and the printed layers underneath. Unlike to previ-
ous reports where the PANI layer has been electrochemically grown, a
binder must be added to promote adhesion and ensure the stability of
printed PANI layer. For this reason, the effect of adding three different
acrylic resins to PANI ink formulations was evaluated in terms of ad-
hesion and wear resistance, but also on printability and sensing perfor-
mance.
Acrylic dispersions were prepared with the aim of ensuring mutual
stability of acrylic and PANI nanofiber dispersions upon mixing, and for-

working electrode and a silver/silver chloride reference electrode. The
glass electrode and the printed electrodes were calibrated with standard
buffer solution of pH 4.01, 7.00 and 10.00.
2.5. Buffer solutions with interferences and artificial sweat
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mation of a flexible film having good adhesion to polyester substrates
upon drying.
PANI inks were formulated considering variables related to jettabil-
ity. For the ink to be jetted, there must be a balance between the capil-
lary forces that hold the ink within the nozzles, the inertial forces that
appear when the ink moves, and the viscous dissipation. The dimension-

Buffer solutions of different pH were prepared according to literature less parameter (Z) defined in the Eq. (1), was proposed as an suitable
[29] (see section 2 of supplementary information for details). Briefly, parameter to predict the jettability as follows [25,26]:
different cation chlorides were added at 0.1 M to buffer solutions of pH
4, 7 and 10 in order to evaluate the response of the sensor to interfer- (1)
ences. For the preparation of solutions of neutral pH with de addition
of Ca2+ and Mg2+, distilled water was used instead of phosphate buffer. in which the surface tension (γ), the viscosity (η) and the density (ρ)
Also, alkaline and acid synthetic sweat solutions were formulated ac-
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cording to ISO 105-E04:2013(E), and they were mixed in different pro-
portions to achieve different pH values. The pH of all the solutions was
measured with the commercial glass electrode.
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are key ink properties that affect jettability. On the other hand, the char-
acteristic length that describes the system is the diameter of the nozzle
(α). For the 10 pL printheads used in this work, this diameter was 20 µm.
These properties and the Z factor are summarized in the Table 1.
According to Derby [33], the drop formation of an ink is suitable if
1 < Z < 10 range. If Z is below 1, the ink is too viscous to allow the

Table 1
Ink properties and calculated Z for PANI inks formulated in this work.

Viscosity Surface tension Density

Ink (mPa s) (mN m−1) pH (g cm−3) Z

PANI-0 1.1 32.5 1.32 0.988 23.0

PANI-R1 1.2 32.1 1.42 0.969 20.8
PANI-R2 1.3 31.7 1.37 0.972 19.1
PANI-R3 1.2 33.3 1.50 0.982 21.3
Fig. 1. Electrode array with the working electrode (located at the center) printed with
PANI-R3 (a) and coated with PANI by electropolymerization (b).

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E. Bilbao et al.
ejection of ink out of the nozzle, since the energy is dissipated. If the Z is
above 10, there is the risk of satellite drops forming. For the inks formu-
lated in this work, Z is around 20. In that way, the SDS helps the print-
ability, since it decreases the surface tension, and hence the Z value.
Since the surface tension is adequate for inkjet printing of ink, the most
reasonable way to lower the Z value would be to add a thickening agent.
However, we were able to inhibit the formation of satellite drops by ad-
justing the waveform of the printhead actuators and thus the addition of
a thickening agent was not necessary in this case. Moreover, comparing
the Z values between PANI-0 and inks with PANI and resins, it could be
concluded that the addition of acrylic resins tend to improve printabil-
ity.
The inks were inkjet-printed up to 2 weeks after formulation with-
out any further treatment. Moreover, the suspension remained stable for
at least 6 months. The drop ejection behavior of the inkjet nozzle was
visually checked using the integrated drop-watcher camera to ensure re-
liable process conditions. The jetting behavior remained stable after 5 h
of continuous printing. Therefore, the formulated PANI inks proved to
be reliable in terms of preventing nozzle clogging during continuous op-
eration and seem to be suitable for printing over long periods of time.
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Fig. 2. Images of the material removed from electrodes in adhesion test. Electrodes: (a) pristine electrode, and printed with (b) PANI-0, (c) PANI-R1, (d) PANI-R2, (e) PANI-R3 and (f)
PANI-EQ.
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Fig. 3. SEM images of PANI-modified electrodes with PANI-0 (a), PANI-R1 (b), PANI-R2 (c), PANI-R3 (d) and PANI-EQ (e) (scale bar = 2 µm).
4
Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
Once formulated and printed, the layers printed with PANI-0,
PANI-R1, PANI-R2 and PANI-R3 were subjected to adhesion (Fig. 2) and
wear resistance tests (Figure S1). Surprisingly, the adhesion test showed
that the printed PANI layers were resistant to adhesion regardless the
addition of acrylic resin, and the tape had removed most of the electro-
chemically grown PANI (PANI-EQ). On the other hand, the wear resis-
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tance was significantly improved by addition of resins. Moreover, it was
observed that PANI-R3 showed the best adhesion and wear resistance
compared to PANI-R1 and PANI R2.
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SEM images were taken in order to analyze de microstructure of the
electrodes. A fibrous and porous structure was present covering the sur-
face of every electrode. Such microstructure is consistent with the pres-
ence of PANI in the form of nanofibers. For PANI-0 (Fig. 3a) SDS is par-
tially covering the voids between the PANI nanofibers leading to a rel-
atively smooth surface. The inclusion of acrylic resins to the ink formu-
lation leaded to formation of a more porous microstructure (Fig. 2b–d)
which can be attained to the coalescence of polymer micelles during
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film formation. For case of PANI-EQ, (Fig. 3e) a porous structure with
submicron-diameter PANI fibers, larger than those incorporated to ink
formulations, can be distinguished.
E. Bilbao et al.
3.2. Performance of printed pH sensors
The potential between working and SPRE electrodes was measured
using different buffer solutions between pH 3 and 11 for all PANI elec-
trodes. This pH range was chosen because these printed sensors can be
integrated to wearables and wound dressing for monitoring the pH of
physiological fluids that fall well within this range. However, the SPRE
electrode did not prove to be suitable enough for such measurements,
since its potential varies with chloride concentration, thus affecting the
reproducibility of the device. It has been reported that such problem can
be solved by coating the printed reference electrode with a polyvinylbu-
tyral membrane saturated with NaCl [34]. However, we have decided
to focus on the working electrode and perform the measurements us-
ing an external reference electrode in order to minimize the potential
sources of variability. Therefore, we measured the potential between
PANI working electrodes and a saturated calomel reference. In these
cases, the response was shown to be linear with pH and similar among
all treatments (Fig. 3). The averages for sensitivity and E0 from the cali-
bration of three different electrodes for each treatment are presented in
Table 2.
The sensitivity to pH in every case was around 63−66 mV with a
clear linear behavior without significant differences between different
electrodes. It could be noticed that the sensitivity of the electrodes was
not significantly affected whether the PANI active layer was printed
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alone or with the addition of acrylic resins. Moreover, the sensitivity for
PANI electrodes fabricated by electropolymerization turned to be lower
than those with PANI deposited by inkjet printing and in accordance to
the sensitivity reported by Guinovart et al. [7]. A potential drift in the
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acidic region was present during the first measurements with the as-pre-
pared electrodes when they were printed (Figure S5). However, this ef-
fect disappeared when the sensors were stored for 30 min in buffer so-
lution of pH 7, showing a linear behavior within our measurement win-
dow (pH 3–11).
Regarding the reproducibility of the electrodes fabricated by deposi-
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tion of PANI by inkjet printing, the printing process could guarantee a
uniform sensitivity above 60 mV/pH with a relative standard deviation
below 5% and the presence of acrylic resins of different composition did
not affect the response of the electrodes. For the case of the intercept E°
the dispersion was much higher for both fabrication techniques for the
PANI layer. In fact, the dispersion for the intercept was lower for the
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electrodes fabricated by inkjet printing than for those fabricated by elec-
tropolymerization. External calibration is always necessary for this type
of electrodes so far and more work needs to be done in order to over-
come this limitation. Much of this limitation arises from insufficient re-
producibility of the fabrication of the active layer for the working elec-
trode. Uneven surfaces of the substrates, screen-printed carbon layers
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and distribution of the PANI inks by inkjet printing are possible sources
of variability in the intercept that have to be taken in account for fur-
ther optimization of potentiometric printed pH sensors (Fig. 4).
The addition of resins to ink formulation did not alter the perfor-
mance of the electrode. This result is consistent with the supernernst
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Table 2
Linear response fitting for PANI pH electrodes. The values for E0 and sensitivity are the
average from the calibration of three different electrodes for each treatment.
PANI layer E0 Sensitivity
(mV) (mV/pH)
PANI-0 482 ± 42 64.6 ± 1.5
PANI-R1 509 ± 8 66.5 ± 3.2
PANI-R2 469 ± 30 63.7 ± 1.3
PANI-R3 493 ± 46 63.8 ± 0.3
PANI-EQ 408 ± 65 56.4 ± 3.8
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Fig. 4. Dependence of potential of printed PANI electrodes vs pH, in buffer solutions
PANI-0, PANI-R1, PANI-R2, PANI-R3 and PANI-EQ.
ian sensitivity reported for electrochemical synthesized PANI using chlo-
ride as counterion [35].
In order to analyze the repeatability of the sensor, pH steps were per-
formed, and the response over time was measured (Fig. 5), considering
that the potential stabilized after 5 min. From the plot, it was observed
that the response of all printed PANI electrodes was repeatable, showing
no drift in the stabilized potential, and negligible hysteresis when pre-
vious measures were performed in acid and alkaline media (see section
4.4 of the supplementary information). In fact, the variation in potential
at pH around 7 represents less than 0.1 pH units. Regarding the response
time, the sensors with acrylic binder took more time to achieve a stable
signal, particularly at high pH. The response of the electrodes printed
with PANI-0 (no resin added) was almost immediate at pH 3 and 11,
but it took almost 50 s to stabilize at pH 7. The addition of acrylic resins
led to longer stabilization times at pH 3 and 11. This effect could be
achieved by the fact that the resin may swell and hamper the diffusion
of hydronium ions within the printed PANI layer.
In order to prove the selectivity of the printed PANI layers to hydro-
nium ions, the response of the potential vs pH was measured in buffer in
presence of sodium, potassium, calcium, magnesium and lithium (Fig.
6), and also in synthetic sweat (Fig. 7).
The response obtained with the sensor in presence of buffer with ad-
dition of different cations is comparable to the obtained without cations
for all printed sensors, with or without acrylic resins added. The sen-
sitivity of the PANI electrode fabricated by electropolymerization was
slightly diminished when Mg2+ was added to the sample. Hence, the
electrodes fabricated by inkjet printing showed better performance in
terms of selectivity of protons against typical cations in concentrations
up to 100 mM, even if resins are added to the ink formulation.
The electrode response was not affected by the presence of synthetic
sweat, showing that the presence of components such as amino acids
does not interfere with the response. This is a promising result that
could be extended with further studies to other physiological samples
such as plasma or urine.
After testing the selectivity with different types of interferences, the
response of the sensors was tested again two years after being stored in
a drawer in our laboratory, to evaluate the stability of the PANI layer
after a long period of time. In Table 3, the sensitivity and E0 obtained
from calibration of the electrodes after two years are shown. This val-
ues for PANI-R1 and PANI-R3 did not change significantly. Surprisingly,
they increased for PANI-0 and PANI-R2.
Ideal sensitivity for potentiometric electrodes can be linked to Nern-
stian behavior and is usually around 59.2 mV/pH for monovalent
E. Bilbao et al.
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Fig. 5. Response of PANI printed electrodes to pH steps in order to evaluate their repeatability: PANI-0 (a), PANI-R1 (b), PANI-R2 (c) and PANI-R3 (d).
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Fig. 6. Response of sensors printed with (a) PANI-0, (b) PANI-R1, (c) PANI-R2, (d) PANI-R3 and (e) PANI-EQ in presence of different ions and pH. Filled points correspond to buffer
solutions without added salts, and hollows points correspond to buffer solutions with addition of different cation chlorides.
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cations. In most cases, practical sensitivity of the electrodes is dimin-
ished due to different issues, including materials, device design and
processes (i.e.: interfering substrates, impurities and other materials de-
posited along with the active material, high contact resistance between
materials, inadequate layer thickness and homogeneity, etc.). In our
case, a maximum sensitivity of 69.1 mV/pH has been achieved for re-
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cently printed electrodes, and up to 78 mV/pH after aging. Storage of
printed electrodes did not provoke a decrease in sensitivity. On the con-
trary, sensitivity increased noticeably after two years for PANI-0 and
PANI-R2 and remained similar for PANI-R1 and PANI-R3. The standard
deviation of sensitivity increased as well in all cases (almost to a rela-
tive 10 % for PANI-R2). E° also increased remarkably for PANI-0 and
PANI-R2 after two years.
Sensitivities above 59.2 mV/pH (so called super-Nernstian behav-
ior) can be achieved by controlling the ratio of hydronium ions to
electrons exchanged in the redox reaction between leucoemeraldine,
emeraldine and pernigraniline forms of PANI. It is known that the de
6
Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
F
OO
PR
pendence of equilibrium potential of PANI with pH is greater in strong
acid media (pH < 1) than at higher pH due to an extra hydronium ion
exchanged by half of the nitrogen atoms of the leucoemeraldine form.
It has been reported that the use of camphorsulfonic acid as counterion
[2] or the preparation of self-doped PANI by electropolymerization un-
der certain conditions [1] can extend this greater dependence of poten-
tial variation to higher pH by means of internal association of dopant
moieties to exchangeable hydronium ions within the PANI film struc-
ture. In our case, since SDS can serve as a dopant and slow rearrange-
ment of polymer chains and nanoparticles can occur during storage, it is
possible that both the increased sensitivity and E0 after two years could
be provoked by polymer and dopant rearrangements within the printed
films. This is a very interesting effect that needs to be analyzed in depth
in future research in order to optimize the sensitivity, reproducibility
and shelf life of printed PANI potentiometric electrodes.
Many materials and fabrication methods can be used for the fabri-
cation of pH-sensitive electrodes/microelectrodes. Moreover, different
E. Bilbao et al. Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx

F
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PR
Fig. 7. Response of sensors printed with PANI-0 (a), PANI-R1 (b), PANI-R2 (c), PANI-R3 (d) and PANI-EQ (e) in presence of synthetic sweat of different pH.

Table 3 4. Conclusions

D
Linear response fitting for printed PANI pH electrodes 2 years after fabrication.

PANI layer E0 Sensitivity R2 The effect of using acrylic resins in aqueous-based PANI ink for-
mulations to print pH-sensitive electrodes was studied. Regarding the
TE
(mV) (mV/pH) ink formulation, the addition of acrylic resins had a positive impact
on the printability and the properties of the layer. Although most of
PANI-0 694 ± 34 77.8 ± 4.5 0.993
PANI-R1 507 ± 20 64.2 ± 4.5 0.990
the printability improvement came from the addition of SDS, acrylic
PANI-R2 700 ± 55 78.0 ± 7.5 0.981 resins had a slight impact on viscosity, which in turn led to lower Z
PANI-R3 440 ± 33 59.8 ± 4.5 0.988 values. Although layer adhesion was not greatly affected, the acrylic
resins significantly improved the wear resistance. Surprisingly, the ad-
EC

sensing techniques may be applied. Some examples are shown in Table
4. A relevant goal for most of these approaches was the fabrication of
low-cost, flexible and reliable electrodes with the best possible sensi-
tivity. Although electropolymerized PANI is an excellent material given
its stability and sensitivity, we proved that PANI can also be applied
RR
hesion of the electropolymerized PANI layer was worse than that of the
printed PANI layers. Regarding sensing properties, the electrodes fab-
ricated with printed PANI layers showed a slightly higher sensitivity
than those of electropolymerized PANI, showing that neither the deposi-
tion method nor the addition of resins affected their sensitivity towards
pH. Moreover, the variability in standard potentials was similar inde-

by inkjet printing. Moreover, these pH electrodes are easier to fabricate pendently of the ink composition and the fabrication technique (inkjet
using scalable printing techniques, and include additives that improve printing or electropolymerization). However, higher reproducibility is
their wear resistance. still necessary in order to avoid the need for individual calibration. The

Table 4
Comparison of different film-based pH sensors.
CO

Active material Sensing method Deposition method Substrate Sensitivity Range (pH) Reference

IrOx ISFET Electrochemical, onto evaporated gold electrodes PEN 9.5 µA/pH 5 – 7.5 [18]
PANI ISFET Electrochemical, onto evaporated gold electrodes PEN 5.25 µA/pH 5 – 7.5 [18]
Carbon/Alizarin Voltammetric Screen printing PVC 55.82 mV/pH 2 – 10 [36]
PANI Potentiometric Electrochemical, onto screen-printed carbon electrodes Adhesive bandage 59.2 mV/pH 2.69 – 7.47 [7]
Oxidized carbon Voltammetric Chemical oxidation of carbon screen-printed electrodes Polyester 57 mV/pH 1.76 – [37]
13.12
UN

Oxidized CNTs Resistance Aerosol jet Kapton® 59.17 kΩ/pH 4 – 10 [38]

CuO nanorods Impedance Screen printing PET 0.64 µF/pH 5 – 8.5 [39]
Oxidized CNTs Potentiometric Inkjet Glass 48.1 mV/pH 3 – 11 [40]
PdO Potentiometric Thermal oxidation of inkjet-printed Pd electrodes Glass 60.6 mV/pH 4 – 10 [41]
PANI Potentiometric Drop casting Polymer-coated 50 mV/pH 4 – 10 [6]
paper
RGO/IrO2 Potentiometric Drop casting (RGO), then electrochemical (IrO2) – 61.71 mV/pH 2 – 12 [42]
IrO2 Potentiometric Electrochemical Stainless steel mesh 47.54 mV/pH 4–8 [10]
RuOx Potentiometric Spin coating ITO on PET 65.11 mV/pH 2 – 12 [43]
PANI Potentiometric Electrochemical FTO on glass 66.7 mV/pH 2–8 [44]
PANI Potentiometric Inkjet printing of PANI ink onto screen-printed carbon Valox® 69.1 mV/pH 3 – 11 This work
electrodes

7
E. Bilbao et al.
electrodes fabricated by inkjet printing were also accurate for measur-
ing pH in the presence of possible interferences, such as cations and
more complex matrices such as simulated sweat. Regarding repeatabil-
ity, the response of the electrode to pH changes was highly repeatable
for all electrodes with printed PANI. Response time was affected by the
presence of acrylic resins, although a longer response time was a minor
drawback compared to the benefits of better printability and layer prop-
erties. Moreover, electrodes fabricated by inkjet printing PANI inks with
acrylic resins R1 and R3 onto screen-printed carbon electrodes proved to
be stable for long periods of time stored in a drawer and maintain their
sensitivity and standard potentials after two years. In conclusion, we
were able to fabricate a pH-sensitive electrode using only printing tech-
niques, by inkjet printing an aqueous-based PANI ink with acrylic resins
onto screen-printed carbon electrodes. These electrodes showed compa-
rable performance to a similar electrode fabricated by electropolymer-
ization of PANI onto screen-printed carbon electrodes and superior sen-
sitivity compared to some recent examples from literature.
Uncited references
[31,32].
CRediT authorship contribution statement
Emanuel Bilbao: Methodology, Validation, Investigation, Data
curation, Writing – original draft. Sunil Kapadia: Methodology,
D
Validation, Investigation. Verónica Riechert: Methodology,
Investigation, Writing – original draft. Javier Amalvy:
Conceptualization, Writing – review & editing, Resources, Funding
TE
acquisition. Fabricio N. Molinari: Formal analysis, Visualization.
Mariano M. Escobar: Conceptualization, Resources. Reinhard R.
Baumann: Resources, Supervision, Project administration, Funding
acquisition. Leandro N. Monsalve: Conceptualization, Writing –
review & editing, Resources, Supervision, Project administration,
Funding acquisition.
EC
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
RR
Acknowledgments
The authors are grateful to INTI, CONICET (PIP 11220150100967),
ANPCyT (PICT 2014-3748, PICT 2017-2787), UTN PID 4769 and BMBF
(MinCyT-BMBF AL17/06) for financial support. Authors are also thank-
ful to Soledad Pereda for the aquisition of SEM images. MME and LNM
CO
are CONICET staff members and JIA of CICPBA. Emanuel Bilbao thanks
CONICET and Universidad Nacional del Oeste for his scholarship.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.snb.2021.130558.
UN
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RR
Emanuel Bilbao is a chemical engineer, graduated from Universidad
Tecnológica Nacional and Associate Professor of Physical Chemistry at
the same University. He is currently working on his Ph D thesis at In-
stituto Nacional de Tecnología Industrial (INTI) under the direction of
Dr. Monsalve. His research involves the formulation of inks based on
polyaniline, and the development of devices and sensors by printing
methods.
CO
Sunil Kapadia is Master of Science at TU Chemnitz, and worked in
Digital Printing and Imaging Technology of the Technische Universität
Chemnitz, Germany.
Verónica Riechert is a chemical engineering from Universidad Na-
cional del Sur (UNS), who obtained her PhD from the same university
UN
in 2017, working in Planta Piloto de Ingeniería Química (PLAPIQUI)
under Prof. Lidia Quinzani and Prof. Marcelo Failla. She did pos-doc-
toral researches in Instituto Nacional de Investigaciones Fisicoquímicas
Teóricas y Aplicadas (INIFTA) under Prof. Javier Amalvy, one of them
related with inks for printed electronics. Riechert is currently working
Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
in Petroquímica Cuyo S.A.I.C as Head of Advanced Materials Develope-
ment.
Javier Amalvy received his Ph.D. in Chemistry from the University
of La Plata in 1984. He is Superior Researcher of Comisión de Inves-
tigaciones Científicas of Buenos Aires Province (CIC), head of Centro
F
de Investigación y Desarrollo en Ciencias y Tecnología de Materiales
(CITEMA), full professor of Polymer at National Technological Univer-
sity (UTN) and adviser at the Fundación Argentina de Nanotecnología
OO
(FAN), Argentina. His research focuses on the synthesis and characteri-
zation of new polymeric materials and nanomaterials. Other research in-
terests comprise environmental issues, like microplastics and pesticides.
He has authored or coauthored over 100 peer-reviewed journal articles,
2 patents and several national standards (IRAM).
Fabricio Molinari was born in Buenos Aires, Argentina. He is a chem-
ical engineer graduated from Universidad Tecnológica Nacional and as-
PR
sociate professor of General Chemistry and Fundamentals of Informatics
in the same University. He is currently working on his PhD thesis at In-
stituto Nacional de Tecnología Industrial, Argentina under the direction
of Dr. Monsalve; and is currently working as an integrated researcher at
the same institution. His current research interests focus on functional
fibers produced by electrospinning technique for scaffolds for tissue en-
gineering, sensors and microelectronics and energy applications.
Mariano Escobar was born in Buenos Aires, Argentina. He obtained
his PhD in 2009 from Buenos Aires University (UBA), Argentina, un-
der Prof. S. Goyanes and Roberto Candal. He joined Instituto Nacional
de Tecnología Industrial, Buenos Aires, as Researcher of CONICET. He
is currently director of Advanced Materials Department. His current re-
search interests focus on polymer and composites materials.
Prof. Reinhard R. Baumann is Emeritus Professor for Digital Print-
ing and Imaging Technology of the Technische Universität Chemnitz,
Germany. Since his engagement in the graphic arts industry, he is in-
volved in the R&D of digital fabrication processes and equipment for the
industrialization of printed and large area electronics. Prof. Baumann
serves since 2004 on the board of the Organic Electronic Association
oe-a. 2011–2015 he served as Vice President of IS&T and is a fellow of
that organization. The results of his research activities are published in
numerous journals, conference papers and patents.
Leandro Monsalve Adjunct Researcher at CONICET, Professional staff
at the Department of Functional Nanomaterials of INTI, and Assistant
professor at UNSAM. He is M.Sc.Chem. (UBA, 2006) and Ph.D. of the
University of Buenos Aires, in the Area of Organic Chemistry (UBA,
2009). Dr. Monsalve performed his doctoral research in the applica-
tion of enzymes in organic synthesis and his postdoctoral research about
preparation and characterization of nanostructured polymeric compos-
ite materials. His current research interests are the development of con-
ductive nanostructured materials processable by electrospinning and
printing techniques, such as flexography and inkjet for in flexible elec-
tronics, biosensors and biointerfaces.