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Pagination SNB 130558
Pagination SNB 130558
Pagination SNB 130558
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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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pH measurements can be used for the analysis of parameters of clinical particles that are insoluble in most solvents. Therefore, the efforts for
relevance including glucose [1–3], triglycerides [4] and wound healing enh6ancing its processability are focused on controlling particle size and
monitoring [5–7]. Moreover, pH of skin can be a useful physiological dispersability. For instance, it is possible to obtain well dispersed PANI
parameter for preventing dehydration during exercise and skin disor- nanofibers in acidic medium by performing the polymerization reaction
ders [8–10]. For these reasons, the development of small and low-cost in solution at 60 °C [12], or nanospheres if the reaction is carried away
pH sensors that could be fabricated at large scale (i.e.: by printing tech- in emulsion [13]. These nanoparticles were successfully used for the
niques) are highly desirable. preparation of inkjet inks for printing ammonia sensors [14], superca-
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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. Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
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to pH 8 by dissolving PANI with camphorsulfonic acid in chloroform Hydrochloric acid and lithium chloride were acquired from Anedra (Ar-
and using the solution for coating glassy carbon electrodes by drop cast- gentina). Potassium persulphate (K2S2O8 KPS), sodium dodecyl sulfate
ing [2]. Since then, the fabrication and characterization of pH sensing (CH3(CH2)11SO4Na SDS), potassium biphthalate (HOOCC6H4COOK), bo-
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devices based either on conductivity [18] or potential [6,7] have been rax (Na2B4O7·10H2O), potassium dihydrogen phosphate (KH2PO4), dis-
developed. However, PANI-based potentiometric pH sensing electrodes odium hydrogen phosphate (Na2HPO4), sodium chloride (NaCl), potas-
fabricated onto flexible substrates using carbon inks as conductive layer sium chloride (KCl), magnesium chloride hexahydrate (MgCl2·6H2O),
material presented diminished sensitivity below 60 mV/pH. This could calcium chloride (CaCl2), and sodium hydroxide (NaOH) were pur-
be due to the presence of interferences that contribute to the redox po- chased from Biopack (Argentina). Buffer solutions of pH 4.01, 7 and
tential at the active layer. 10 (20 °C) traceable to SRM from NIST and PTB were purchased from
PANI layers can be deposited by inkjet printing, which is a fast, re- Merck. Ethyl acrylate (CH2 = CHCOOC2H5, EA) from Fluka, methyl
producible and scalable method for depositing functional patterns, by methacrylate (CH2 = C(CH3)COOCH3, MMA) and methacrylic acid
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three different approaches: a) printing of monomer and polymerization (CH2 = C(CH3)COOH, MAA) from Sigma Aldrich, and ethylene gly-
once printed [19,20], b) dissolution of PANI in organic solvents [21,22] col dimethacrylate (CH2 = C(CH3)COOCH2CH2OCOC(CH3) = CH2,
and c) dispersion of PANI nanoparticles in aqueous media [3,23,24]. EGDMA) from Merck.
Aqueous-based inks are the most desirable due to their safety and low
environmental impact. However, special care must be taken for ensuring 2.2. Ink formulation
printability and mechanical stability of the PANI layer in any case. For
this, the particle size and concentration must be controlled and other A suspension containing 4 mg mL−1 of PANI nanofibers was synthe-
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non-volatile additives such as film-forming resins and stabilizers must sized according to the method described by Kaner [12] (see supplemen-
be added for dispersion. tary material for details). The suspension was stabilized with 8 mg mL−1
Acrylic resins are a group of thermoplastic substances derived from of SDS, and this suspension was nominated PANI-0.
acrylic acid, methacrylic acid, and other related compounds. More Three waterborne acrylic resins were obtained by semicontinuous
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specifically, water-based acrylic dispersions are used in its dispersed emulsion polymerization. Resins contain mainly EA and MMA in dif-
form for textile finishes, adhesives, lacquer, and printing inks. They pro- ferent ratios, achieving up to 98 wt.% of total monomer content. As
vide adhesion and mechanical stability to the printed layer. Moreover, EA/MMA mass ratio increase, glass transition temperature of resin de-
they are safer and more environmentally friendly than solvent-based crease. Additionally, they contain up to 3 wt.% of MAA and ∼0.1 wt.%
formulations. However, most commercial acrylic dispersion formula- of EGDMA (Table S1). Increasing MAA content, pH of the final disper-
tions developed for inkjet printing inks are slightly alkaline, which sion goes down and the amount of −COOH increases, expecting a bet-
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make them unsuitable for formulations containing conductive polymers ter adhesion to the substrate. On the other hand, EGDMA acts as poly-
such as polyaniline (PANI) [25]. Moreover, the colloidal stability of mers crosslinker to improve mechanical properties. The initial charge of
both acrylic latex nanoparticles and conductive polymer nanoparticles is monomers in reactor is defined based on the desired EA/MMA ratio in
compromised. To overcome this problem, custom-made acrylic binders the resin, taking into account the reactivity ratio of monomers [27]. In
must be formulated. For instance, Wang et al. prepared an hydrogel all synthesis, reactor is initially charged with all EA (monomer with less
made of PANI, polyacrylic acid and phytic acid that presented improved reactivity), a fraction of MMA and EGDMA, emulsifier (SDS) and dis-
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adhesion onto silicon-based anodes in lithium-ion batteries [26]. tilled water (Table S2).
For the fabrication of pH-sensitive electrodes using printing tech- The dispersion was stirred at 270 rpm during 30 min, while it is
niques, electrodeposition of the active layer onto conductive printed heated to 60 °C with nitrogen gas passing through the bulk to elimi-
electrodes is the most common method so far. Electrodeposition ensures nate dissolved oxygen. After that, the initiator (KPS) dissolved in a small
layer homogeneity, purity and mechanical stability of the active layer. amount of water was added to the reactor and, after 15 min of reac-
However, little is known about the sensing properties of printed pH-sen- tion, a monomer feed was added to the reactor at 2 g/min. The feed is
sitive electrodes with electrodeposited active layer compared to printed
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on top. Moreover, screen-printed carbon electrodes modified with PANI aliquot of PANI-0 to fulfill a weight ratio PANI:resin of 1:1 on dry basis,
by electropolymerization were made for comparing their pH sensing resulting in inks PANI-R1, PANI-R2 and PANI-R3, with a solids content
properties. The printability of the PANI inks, the mechanical properties of 16 mg mL−1.
of the PANI layer and the performance of the electrodes for pH sensing The surface tension was measured by the Du Noüy method with a
were also investigated. Attension Sigma 700 force tensiometer. Viscosity was measured with a
rotatory viscometer Myr VR 3000 series, at 264 s−1 shear rate.
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E. Bilbao et al. Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
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.
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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- 3. Results and discussion
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 3.1. Ink formulation and characterization
PANI inks were printed on top of the working electrodes with 2540 dpi
resolution with a Dimatix 2850 Materials Printer (Fujifilm, USA) using All PANI inks were formulated from a stable aqueous dispersion of
DMC 11,610 cartridges. Each cartridge has a reservoir of capacity of PANI nanofibers. However, this dispersion was not suitable for inkjet
1.5 mL and a piezoelectric printhead with 16 nozzles linearly spaced printing since printheads tended to clog with this dispersion and the
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at 254 microns with typical drop volume of 10 picoliters. Considering layers of deposited PANI showed poor adhesion and homogeneity. The
this nominal volume of the drop, the printing resolution and the area of addition of SDS to the aqueous dispersion for inkjet printing seemed
the working electrode printed with PANI inks (a circle of 1 mm diame- to be a useful strategy because it stabilizes the dispersion and reduces
ter = 0.79mm2), about 0.079 microliters of ink are consumed for print- its surface tension. Moreover, it has been successfully used in previous
ing each layer on an individual electrode. Pictures of a fully printed elec- works for the formulation of inkjet inks from aqueous-based dispersions
trode and an electrode fabricated by electropolymerization are shown in [3,23,24]. For this reason, we added 8 mg/mL of SDS to the PANI aque-
Fig. 1a and b respectively. ous dispersion to improve printability. Moreover, since the PANI layer
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on the pH electrodes is exposed, it should present good adhesion to
2.4. Electrochemical characterization the plastic substrate and the printed layers underneath. Unlike to previ-
ous reports where the PANI layer has been electrochemically grown, a
Potentiometric measurements were performed with a potentiostat binder must be added to promote adhesion and ensure the stability of
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Teq4 (Nanotec, Argentina) by measuring the open circuit potential be- printed PANI layer. For this reason, the effect of adding three different
tween the working electrode and a saturated calomel electrode (SCE) acrylic resins to PANI ink formulations was evaluated in terms of ad-
as reference electrode (input impedance > 1012 ohm). A more detailed hesion and wear resistance, but also on printability and sensing perfor-
description of the measuring configuration is presented in sections 4.1 mance.
and 4.2 of the supplementary information. The pH of the test solutions Acrylic dispersions were prepared with the aim of ensuring mutual
was measured with a Sanxin MP512 pH meter equipped with a glass stability of acrylic and PANI nanofiber dispersions upon mixing, and for-
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working electrode and a silver/silver chloride reference electrode. The mation of a flexible film having good adhesion to polyester substrates
glass electrode and the printed electrodes were calibrated with standard upon drying.
buffer solution of pH 4.01, 7.00 and 10.00. PANI inks were formulated considering variables related to jettabil-
ity. For the ink to be jetted, there must be a balance between the capil-
2.5. Buffer solutions with interferences and artificial sweat lary forces that hold the ink within the nozzles, the inertial forces that
appear when the ink moves, and the viscous dissipation. The dimension-
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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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are key ink properties that affect jettability. On the other hand, the char-
cording to ISO 105-E04:2013(E), and they were mixed in different pro- acteristic length that describes the system is the diameter of the nozzle
portions to achieve different pH values. The pH of all the solutions was (α). For the 10 pL printheads used in this work, this diameter was 20 µm.
measured with the commercial glass electrode. 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
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Table 1
Ink properties and calculated Z for PANI inks formulated in this work.
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E. Bilbao et al. Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
ejection of ink out of the nozzle, since the energy is dissipated. If the Z is Once formulated and printed, the layers printed with PANI-0,
above 10, there is the risk of satellite drops forming. For the inks formu- PANI-R1, PANI-R2 and PANI-R3 were subjected to adhesion (Fig. 2) and
lated in this work, Z is around 20. In that way, the SDS helps the print- wear resistance tests (Figure S1). Surprisingly, the adhesion test showed
ability, since it decreases the surface tension, and hence the Z value. that the printed PANI layers were resistant to adhesion regardless the
Since the surface tension is adequate for inkjet printing of ink, the most addition of acrylic resin, and the tape had removed most of the electro-
reasonable way to lower the Z value would be to add a thickening agent. chemically grown PANI (PANI-EQ). On the other hand, the wear resis-
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However, we were able to inhibit the formation of satellite drops by ad- tance was significantly improved by addition of resins. Moreover, it was
justing the waveform of the printhead actuators and thus the addition of observed that PANI-R3 showed the best adhesion and wear resistance
a thickening agent was not necessary in this case. Moreover, comparing compared to PANI-R1 and PANI R2.
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the Z values between PANI-0 and inks with PANI and resins, it could be SEM images were taken in order to analyze de microstructure of the
concluded that the addition of acrylic resins tend to improve printabil- electrodes. A fibrous and porous structure was present covering the sur-
ity. face of every electrode. Such microstructure is consistent with the pres-
The inks were inkjet-printed up to 2 weeks after formulation with- ence of PANI in the form of nanofibers. For PANI-0 (Fig. 3a) SDS is par-
out any further treatment. Moreover, the suspension remained stable for tially covering the voids between the PANI nanofibers leading to a rel-
at least 6 months. The drop ejection behavior of the inkjet nozzle was atively smooth surface. The inclusion of acrylic resins to the ink formu-
visually checked using the integrated drop-watcher camera to ensure re- lation leaded to formation of a more porous microstructure (Fig. 2b–d)
liable process conditions. The jetting behavior remained stable after 5 h which can be attained to the coalescence of polymer micelles during
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of continuous printing. Therefore, the formulated PANI inks proved to film formation. For case of PANI-EQ, (Fig. 3e) a porous structure with
be reliable in terms of preventing nozzle clogging during continuous op- submicron-diameter PANI fibers, larger than those incorporated to ink
eration and seem to be suitable for printing over long periods of time. formulations, can be distinguished.
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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).
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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
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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
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Fig. 4. Dependence of potential of printed PANI electrodes vs pH, in buffer solutions
all treatments (Fig. 3). The averages for sensitivity and E0 from the cali- PANI-0, PANI-R1, PANI-R2, PANI-R3 and PANI-EQ.
bration of three different electrodes for each treatment are presented in
Table 2. ian sensitivity reported for electrochemical synthesized PANI using chlo-
The sensitivity to pH in every case was around 63−66 mV with a ride as counterion [35].
clear linear behavior without significant differences between different In order to analyze the repeatability of the sensor, pH steps were per-
electrodes. It could be noticed that the sensitivity of the electrodes was formed, and the response over time was measured (Fig. 5), considering
not significantly affected whether the PANI active layer was printed that the potential stabilized after 5 min. From the plot, it was observed
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alone or with the addition of acrylic resins. Moreover, the sensitivity for that the response of all printed PANI electrodes was repeatable, showing
PANI electrodes fabricated by electropolymerization turned to be lower no drift in the stabilized potential, and negligible hysteresis when pre-
than those with PANI deposited by inkjet printing and in accordance to vious measures were performed in acid and alkaline media (see section
the sensitivity reported by Guinovart et al. [7]. A potential drift in the 4.4 of the supplementary information). In fact, the variation in potential
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acidic region was present during the first measurements with the as-pre- at pH around 7 represents less than 0.1 pH units. Regarding the response
pared electrodes when they were printed (Figure S5). However, this ef- time, the sensors with acrylic binder took more time to achieve a stable
fect disappeared when the sensors were stored for 30 min in buffer so- signal, particularly at high pH. The response of the electrodes printed
lution of pH 7, showing a linear behavior within our measurement win- with PANI-0 (no resin added) was almost immediate at pH 3 and 11,
dow (pH 3–11). but it took almost 50 s to stabilize at pH 7. The addition of acrylic resins
Regarding the reproducibility of the electrodes fabricated by deposi- led to longer stabilization times at pH 3 and 11. This effect could be
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tion of PANI by inkjet printing, the printing process could guarantee a achieved by the fact that the resin may swell and hamper the diffusion
uniform sensitivity above 60 mV/pH with a relative standard deviation of hydronium ions within the printed PANI layer.
below 5% and the presence of acrylic resins of different composition did In order to prove the selectivity of the printed PANI layers to hydro-
not affect the response of the electrodes. For the case of the intercept E° nium ions, the response of the potential vs pH was measured in buffer in
the dispersion was much higher for both fabrication techniques for the presence of sodium, potassium, calcium, magnesium and lithium (Fig.
PANI layer. In fact, the dispersion for the intercept was lower for the 6), and also in synthetic sweat (Fig. 7).
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electrodes fabricated by inkjet printing than for those fabricated by elec- The response obtained with the sensor in presence of buffer with ad-
tropolymerization. External calibration is always necessary for this type dition of different cations is comparable to the obtained without cations
of electrodes so far and more work needs to be done in order to over- for all printed sensors, with or without acrylic resins added. The sen-
come this limitation. Much of this limitation arises from insufficient re- sitivity of the PANI electrode fabricated by electropolymerization was
producibility of the fabrication of the active layer for the working elec- slightly diminished when Mg2+ was added to the sample. Hence, the
trode. Uneven surfaces of the substrates, screen-printed carbon layers electrodes fabricated by inkjet printing showed better performance in
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and distribution of the PANI inks by inkjet printing are possible sources terms of selectivity of protons against typical cations in concentrations
of variability in the intercept that have to be taken in account for fur- up to 100 mM, even if resins are added to the ink formulation.
ther optimization of potentiometric printed pH sensors (Fig. 4). The electrode response was not affected by the presence of synthetic
The addition of resins to ink formulation did not alter the perfor- sweat, showing that the presence of components such as amino acids
mance of the electrode. This result is consistent with the supernernst 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.
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Table 2 After testing the selectivity with different types of interferences, the
Linear response fitting for PANI pH electrodes. The values for E0 and sensitivity are the response of the sensors was tested again two years after being stored in
average from the calibration of three different electrodes for each treatment. 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
PANI layer E0 Sensitivity
from calibration of the electrodes after two years are shown. This val-
(mV) (mV/pH) ues for PANI-R1 and PANI-R3 did not change significantly. Surprisingly,
they increased for PANI-0 and PANI-R2.
PANI-0 482 ± 42 64.6 ± 1.5 Ideal sensitivity for potentiometric electrodes can be linked to Nern-
PANI-R1 509 ± 8 66.5 ± 3.2
stian behavior and is usually around 59.2 mV/pH for monovalent
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. 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- pendence of equilibrium potential of PANI with pH is greater in strong
ished due to different issues, including materials, device design and acid media (pH < 1) than at higher pH due to an extra hydronium ion
processes (i.e.: interfering substrates, impurities and other materials de- exchanged by half of the nitrogen atoms of the leucoemeraldine form.
posited along with the active material, high contact resistance between It has been reported that the use of camphorsulfonic acid as counterion
materials, inadequate layer thickness and homogeneity, etc.). In our [2] or the preparation of self-doped PANI by electropolymerization un-
case, a maximum sensitivity of 69.1 mV/pH has been achieved for re- der certain conditions [1] can extend this greater dependence of poten-
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cently printed electrodes, and up to 78 mV/pH after aging. Storage of tial variation to higher pH by means of internal association of dopant
printed electrodes did not provoke a decrease in sensitivity. On the con- moieties to exchangeable hydronium ions within the PANI film struc-
trary, sensitivity increased noticeably after two years for PANI-0 and ture. In our case, since SDS can serve as a dopant and slow rearrange-
PANI-R2 and remained similar for PANI-R1 and PANI-R3. The standard ment of polymer chains and nanoparticles can occur during storage, it is
deviation of sensitivity increased as well in all cases (almost to a rela- possible that both the increased sensitivity and E0 after two years could
tive 10 % for PANI-R2). E° also increased remarkably for PANI-0 and be provoked by polymer and dopant rearrangements within the printed
PANI-R2 after two years. films. This is a very interesting effect that needs to be analyzed in depth
Sensitivities above 59.2 mV/pH (so called super-Nernstian behav- in future research in order to optimize the sensitivity, reproducibility
ior) can be achieved by controlling the ratio of hydronium ions to and shelf life of printed PANI potentiometric electrodes.
electrons exchanged in the redox reaction between leucoemeraldine, Many materials and fabrication methods can be used for the fabri-
emeraldine and pernigraniline forms of PANI. It is known that the de cation of pH-sensitive electrodes/microelectrodes. Moreover, different
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E. Bilbao et al. Sensors & Actuators: B. Chemical xxx (xxxx) xxx-xxx
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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
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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
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(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-
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hesion of the electropolymerized PANI layer was worse than that of the
sensing techniques may be applied. Some examples are shown in Table printed PANI layers. Regarding sensing properties, the electrodes fab-
4. A relevant goal for most of these approaches was the fabrication of ricated with printed PANI layers showed a slightly higher sensitivity
low-cost, flexible and reliable electrodes with the best possible sensi- than those of electropolymerized PANI, showing that neither the deposi-
tivity. Although electropolymerized PANI is an excellent material given tion method nor the addition of resins affected their sensitivity towards
its stability and sensitivity, we proved that PANI can also be applied pH. Moreover, the variability in standard potentials was similar inde-
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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.
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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
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acquisition. Fabricio N. Molinari: Formal analysis, Visualization. Chih-Pei Cha, Inkjet-printed energy storage device using graphene/polyaniline inks,
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The authors declare that they have no known competing financial
sensor using organic electrochemical transistors, Int. J. Adv. Mater. Technol.
interests or personal relationships that could have appeared to influence 2 (2017) 1–5, https://doi.org/10.1002/admt.201600141.
the work reported in this paper. [19] L. Li, L. Pan, Z. Ma, K. Yan, W. Cheng, Y. Shi, G. Yu, All Inkjet-Printed Amperomet-
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are CONICET staff members and JIA of CICPBA. Emanuel Bilbao thanks applications, Adv. Funct. Mater. 24 (2014) 3375–3383, https://doi.org/10.1002/
adfm.201303371.
CONICET and Universidad Nacional del Oeste for his scholarship.
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Supplementary material related to this article can be found, in the ducting polyaniline based flexible humidity sensor, Sensors Actuators B Chem.
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[32] Z. Du, Y. Lin, R. Xing, X. Cao, X. Yu, Y. Han, Controlling the polymer ink’s rheolog- of La Plata in 1984. He is Superior Researcher of Comisión de Inves-
ical properties and viscoelasticity to suppress satellite droplets, Polymer (Guildf). tigaciones Científicas of Buenos Aires Province (CIC), head of Centro
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395–414, https://doi.org/10.1146/annurev-matsci-070909-104502. sity (UTN) and adviser at the Fundación Argentina de Nanotecnología
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[34] T. Guinovart, G.A. Crespo, F.X. Rius, F.J. Andrade, A reference electrode based on (FAN), Argentina. His research focuses on the synthesis and characteri-
polyvinyl butyral (PVB) polymer for decentralized chemical measurements, Anal.
Chim. Acta 821 (2014) 72–80, https://doi.org/10.1016/j.aca.2014.02.028. zation of new polymeric materials and nanomaterials. Other research in-
[35] T. Lindfors, A. Ivaska, pH sensitivity of polyaniline and its substituted derivatives, terests comprise environmental issues, like microplastics and pesticides.
J. Electroanal. Chem. 531 (2002) 43–52, https://doi.org/10.1016/S0022- He has authored or coauthored over 100 peer-reviewed journal articles,
0728(02)01005-7. 2 patents and several national standards (IRAM).
[36] C. Dai, P. Song, J.D. Wadhawan, A.C. Fisher, N.S. Lawrence, Screen printed
alizarin-based carbon electrodes: monitoring pH in unbuffered media, Electroanaly-
sis 27 (2015) 917–923, https://doi.org/10.1002/elan.201400704. Fabricio Molinari was born in Buenos Aires, Argentina. He is a chem-
[37] F.E. Galdino, J.P. Smith, S.I. Kwamou, D.K. Kampouris, J. Iniesta, G.C. Smith, J.A. ical engineer graduated from Universidad Tecnológica Nacional and as-
PR
Bonacin, C.E. Banks, Graphite screen-printed electrodes applied for the accurate sociate professor of General Chemistry and Fundamentals of Informatics
and reagentless sensing of pH, Anal. Chem. 87 (2015) 11666–11672, https://doi.
org/10.1021/acs.analchem.5b01236.
in the same University. He is currently working on his PhD thesis at In-
[38] G.L. Goh, S. Agarwala, Y.J. Tan, W.Y. Yeong, A low cost and flexible carbon nan- stituto Nacional de Tecnología Industrial, Argentina under the direction
otube pH sensor fabricated using aerosol jet technology for live cell applications, of Dr. Monsalve; and is currently working as an integrated researcher at
Sensors Actuators, B Chem. 260 (2018) 227–235, https://doi.org/10.1016/j.snb.
the same institution. His current research interests focus on functional
2017.12.127.
[39] L. Manjakkal, B. Sakthivel, N. Gopalakrishnan, R. Dahiya, Printed flexible electro- fibers produced by electrospinning technique for scaffolds for tissue en-
chemical pH sensors based on CuO nanorods, Sensors Actuators, B Chem. gineering, sensors and microelectronics and energy applications.
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263 (2018) 50–58, https://doi.org/10.1016/j.snb.2018.02.092.
[40] Y. Qin, H.J. Kwon, A. Subrahmanyam, M.M.R. Howlader, P.R. Selvaganapathy, A.
Mariano Escobar was born in Buenos Aires, Argentina. He obtained
Adronov, M.J. Deen, Inkjet-printed bifunctional carbon nanotubes for pH sensing,
Mater. Lett. 176 (2016) 68–70, https://doi.org/10.1016/j.matlet.2016.04.048. his PhD in 2009 from Buenos Aires University (UBA), Argentina, un-
[41] Y. Qin, A.U. Alam, S. Pan, M.M.R. Howlader, R. Ghosh, N.X. Hu, H. Jin, S. Dong, der Prof. S. Goyanes and Roberto Candal. He joined Instituto Nacional
TE
C.H. Chen, M.J. Deen, Integrated water quality monitoring system with pH, free de Tecnología Industrial, Buenos Aires, as Researcher of CONICET. He
chlorine, and temperature sensors, Sensors Actuators, B Chem. 255 (2018)
is currently director of Advanced Materials Department. His current re-
781–790, https://doi.org/10.1016/j.snb.2017.07.188.
[42] J. Yang, T.J. Kwak, X. Zhang, R. McClain, W.J. Chang, S. Gunasekaran, Iridium ox- search interests focus on polymer and composites materials.
ide-reduced graphene oxide nanohybrid thin film modified screen-printed elec-
trodes as disposable electrochemical paper microfluidic pH sensors, J. Vis. Exp. Prof. Reinhard R. Baumann is Emeritus Professor for Digital Print-
2016 (2016) 1–7, https://doi.org/10.3791/53339.
ing and Imaging Technology of the Technische Universität Chemnitz,
EC
[43] K. Singh, B.S. Lou, J.L. Her, S.T. Pang, T.M. Pan, Super Nernstian pH response and
enzyme-free detection of glucose using sol-gel derived RuOx on PET flexible-based Germany. Since his engagement in the graphic arts industry, he is in-
extended-gate field-effect transistor, Sensors Actuators, B Chem. 298 (2019) volved in the R&D of digital fabrication processes and equipment for the
126837, https://doi.org/10.1016/j.snb.2019.126837. industrialization of printed and large area electronics. Prof. Baumann
[44] G.D.M. Madeira, H.J.N.P. Dias Mello, M.C. Faleiros, M. Mulato, Model improve-
ment for super-Nernstian pH sensors: the effect of surface hydration, J. Mater. Sci. serves since 2004 on the board of the Organic Electronic Association
56 (2021) 2738–2747, https://doi.org/10.1007/s10853-020-05412-w. 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
RR
Emanuel Bilbao is a chemical engineer, graduated from Universidad numerous journals, conference papers and patents.
Tecnológica Nacional and Associate Professor of Physical Chemistry at
the same University. He is currently working on his Ph D thesis at In- Leandro Monsalve Adjunct Researcher at CONICET, Professional staff
stituto Nacional de Tecnología Industrial (INTI) under the direction of at the Department of Functional Nanomaterials of INTI, and Assistant
Dr. Monsalve. His research involves the formulation of inks based on professor at UNSAM. He is M.Sc.Chem. (UBA, 2006) and Ph.D. of the
polyaniline, and the development of devices and sensors by printing University of Buenos Aires, in the Area of Organic Chemistry (UBA,
methods. 2009). Dr. Monsalve performed his doctoral research in the applica-
CO