Research Article

Cite This: ACS Appl. Mater. Interfaces 2018, 10, 5185−5195 www.acsami.org

Highly Exfoliated MWNT−rGO Ink-Wrapped Polyurethane Foam for

Piezoresistive Pressure Sensor Applications
Amit Tewari,†,‡,∥ Srinivas Gandla,‡ Siva Bohm,§ Christopher R. McNeill,∥ and Dipti Gupta*,†,‡
†
IITB-Monash Research Academy and ‡Department of Metallurgical Engineering and Materials Science, Indian Institute of
Technology Bombay, Powai, Mumbai 400076, India
§
Talga Technologies Ltd., Cambridge Science Park, Unit 15-17 Milton Road, Cambridge CB4 0FQ, United Kingdom
∥
Department of Materials Science and Engineering, Monash University, Wellington Road, Clayton, VIC 3800, Australia
*
S Supporting Information
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ABSTRACT: The fabrication of pressure sensors based on reduced graphene oxide

(rGO) as the sensing material is challenging due to the intrinsic hydrophobic
behavior of graphene oxide inks as well as the agglomeration of graphene oxide flakes
after reduction. Hydrazine (a reducing agent) and a dual-component additive
comprising benzisothiazolinone and methylisothiazolinone in appropriate proportion
were used to synthesize a rGO ink with a hydrophilic nature. Utilizing this
hydrophilic rGO ink mixed with multiwalled carbon nanotubes (MWNTs), a very
simple, low-cost approach is demonstrated for the fabrication of a pressure sensor
based on polyurethane (PU) foam coated with the MWNT−rGO ink (MWNT−
rGO@PU foam). The MWNT−rGO@PU foam-based devices are shown to be
versatile pressure sensors with the potential to detect both small-scale and large-scale
movements. At low pressure (below 2.7 kPa, 50% strain), the formation of
microcracks that scatter electrical charges results in a detectable increase in resistance
suitable for detecting small-scale motion. At a higher pressure, the compressive
contact of the coated faces of the PU foam results in a sharp decrease in resistance suitable for monitoring of large-scale motion.
Moreover, these sensors exhibit good flexibility and reproducibility over 5000 cycles. The versatility of this sensor has been
demonstrated in a wide range of applications, such as speech recognition, health monitoring, and body motion detection. The
significant advantages of this sensor are that its cost is low, it is easy to fabricate, and it has a versatility that renders it favorable to
health-monitoring applications.
KEYWORDS: reduced graphene oxide (rGO), multiwalled carbon nanotubes (MWNTs), polyurethane (PU) foam,
piezoresistive pressure sensor, sensitivity, microcracks

1. INTRODUCTION imperative that alternative routes that are simple and cost-
Flexible and low-cost sensors will have a high demand in the effective be developed for flexible pressure-sensitive materials
future because of their applicability in various applications, such with good sensitivity across the broad pressure domain.
as electronic skin, 1 speech recognition, 2 sport motion Piezoresistive sensors that convert the applied pressure into
monitoring,3 portable healthcare monitoring,4 and prosthetic an electrical signal are considered to be more demanding due to
devices.5 Until now, various pressure-sensing mechanisms have their several advantages, such as low-cost, feasibility of
been proposed, including piezoelectric sensing,6,7 piezoresistive processing, and convenient signal collection.6−8,19 In the past,
sensing,8−10 triboelectric sensing,11 transistor sensing,12−14 and elastomeric conducting composite materials were convention-
capacitive sensing.15,16 Traditional transistor-based sensors, ally used along with carbon black for fabricating piezoresistive
especially those based on silicon metal-oxide semiconductor sensors,8 but these materials had some limitations, such as
field-effect transistors, have demonstrated a high sensitivity. material instability, lack of sensitivity, and nonreproducibility in
However, because of their rigidity, they are incompatible with the low-pressure regime (<10 kPa). Recently, rational
flexible devices. Currently, several flexible pressure sensors have assemblies of micro- and nanoconductive materials have been
been demonstrated that include capacitive sensors with utilized to fabricate sensitive pressure sensors, such as those
microstructured rubber dielectric layers,10 organic field-effect based on polyaniline nanofibers and Au-coated poly-
transistors,12 nanowire active array field-effect transistors,17 and (dimethylsiloxane) (PDMS) micropillars,20 ultrathin gold
reversible interlocking nanofiber piezoresistors.18 The fabrica-
tion processes for these flexible pressure sensors, however, Received: October 9, 2017
typically involve complex processing steps, which impact the Accepted: January 24, 2018
cost of manufacturing sensor-based products. It is therefore Published: January 24, 2018

© 2018 American Chemical Society 5185 DOI: 10.1021/acsami.7b15252

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nanowire-impregnated tissue paper sandwiched between In this work, we therefore have addressed these issues and
PDMS sheets,21 hierarchically compounding polyurethane have developed a simple and direct method for fabricating
(PU) fibers, nylon fibers, Ag nanowires, piezoresistive rubber,3 flexible piezoresistive pressure sensors by employing a water-
and so on.2 Unfortunately, the widespread application of based MWNTs−rGO ink into which commercially available
piezoresistive sensors based on abovementioned materials is PU foam is dipped without the need for subsequent chemical
restricted as their fabrication includes sophisticated processing treatment. The foam-based sensors using the MWNTs−rGO
environments coupled with the use of expensive materials such ink have demonstrated sensitivity values very much comparable
as Ag/Au nanowires and nanoparticles. to those of foam-based sensors having metal sputtered on their
Devices based on conductive porous foams or sponges skeleton35 in the medium pressure range. The rGO ink was
represent a new approach for the fabrication of piezoresistive synthesized from graphene oxide (GO) solution using
pressure sensors enabled by the combination of mechanical hydrazine monohydrate as the reducing agent and a water-
flexibility and electronic conductivity.22 Additionally, their based novel additive, which converted the intrinsic behavior of
production methods are scalable, which makes them an the rGO ink from hydrophobic to hydrophilic. Functionalized
attractive choice for use in devices that require mechanical unzipped MWNTs were synthesized with water as the solvent
transduction. Until now, various conductive sponges (with high using high shear forces36 and added to the rGO ink in an
electrical and good mechanical properties) have been realized appropriate ratio to enhance the electrical conductivity by the
by a variety of routes, including chemical vapor deposition,22 interlinking of flakes wrapped on the PU skeleton. The
cellulose nanofiber sponges,23 and carbonization of hybrid MWNT−rGO ink was infused into the PU foam by repeated
(metal−polymer) nanocable sponges,24 to develop piezoresis- dipping that was followed by thermal drying. This was done to
tive sensors. However, the highly conductive sponges that have have the PU skeleton wrapped with rGO flakes, which resulted
been employed to date for manufacturing pressure sensors have in the final product, the MWNT−rGO@PU (MWNTs−rGO
exhibited low modulus to applied pressure, limiting their ink in PU foam) sensor. A wide range of strains varying from 10
application. to 70% (corresponding to 2.22−16.4 kPa) were applied to the
Moreover, commercially available polyurethane (PU) sensors, and their responses were recorded in real time,
sponges have been utilized for the fabrication of pressure showing good reproducibility. The versatile potential of the
sensors by dipping such PU sponges into solutions dispersed MWNT−rGO@PU pressure sensor is demonstrated in small-
with conductive carbon-based materials, such as carbon black,25 scale motion monitoring applications, such as pulse recognition,
multiwalled carbon nanotubes (MWNTs),26 and graphene voice recognition, and cheek bulging (associated with health
oxide (GO).27 Such sensors based on low-cost PU sponges monitoring) and also in large-scale monitoring applications,
have demonstrated good performance with respect to such as recording finger extension and bending.
sensitivity, pressure range, signal-to-noise ratio, response time,
linearity, and durability. However, it is to be noted that the 2. EXPERIMENTAL SECTION
sensitivity of such sensors in the medium pressure range (2−10
2.1. Material Details. Graphite flakes were supplied by the Talga
kPa), useful for vital sign monitoring is low (0.02−0.03 kPa−1) Resources Ltd., via Talga Advanced Materials GmbH. Hydrogen
when coated with only carbon black,25 carbon nanotube,26 or monohydrate and commercially available PU foams were purchased
reduced graphene oxide (rGO).27 Additionally, to obtain a from Sigma-Aldrich. Sodium nitrate, concentrated sulfuric acid (98%
good dispersion of these nanomaterials, often stabilizers/ pure), potassium permanganate, and hydrogen monohydrate (35%
dispersing agents are used, which reduce the conductivity of aqueous) were purchased from Merck. The additive material
coatings using these materials. For example, in the case of rGO- (benzisothiazolinone and methylisothiazolinone) was bought from
based foam sensors, GO has been employed as the starting the BYK Company (Germany) and MWNTs from NANOCYL
material, which is further reduced via chemical treatment. (NC7000 series).
2.2. Synthesis of GO and rGO. GO was initially synthesized
Because it is challenging to obtain a highly dispersive and according to the modified Hummers method.37 The prepared GO
conductive solution of rGO (without using any stabilizer28−30) solution (20 mL) at a concentration of 0.5 mg/mL was then
following reduction due to the flocculation of rGO flakes, a ultrasonicated continuously for 45 min to obtain a highly dispersed
two-step procedure is commonly reported. Here, the foams GO solution. Thereafter, hydrazine monohydrate and a dual-
were repeatedly dipped in the GO solution and thereafter component additive composed of benzisothiazoline and methyliso-
reduced using different reduction techniques, such as acid thiazolinone were added in 5:1 ratio by volume. Hydrazine served as a
reduction,27,31 microwave reduction,32 thermal reduction,33 reducing agent, whereas the additive helped in inhibiting the
etc., to obtain rGO. It is to be noted that these reduction agglomeration of rGO graphene flakes. The prepared solution was
processes may deteriorate the intrinsic properties of the base then kept in a vacuum oven in a glass vial for 24 h at 90 °C to obtain a
highly dispersive rGO ink. The formation of rGO was confirmed when
material and thus are not strictly suitable. In view of these the GO solution changed from light yellow to deep black after
limitations, simplifying the manufacturing process to avoid the reduction. The prepared rGO ink was then allowed to cool naturally
need for chemical treatment of the coated sponge would and was further used in the making of sensors.
represent a significant step forward and may also result in 2.3. Synthesis of Functionalized MWNTs and MWNTs−rGO
improved performance. Furthermore, it might also be beneficial Ink. The synthesis of functionalized unzipped MWNTs has already
to introduce a structural change27 or incorporate conductive been reported in our previous work.36 Because the conductivity
materials such as MWNTs along with rGO flakes within the obtained through the pure rGO film (0.02 mS/cm) was very low,
foam to enhance its sensitivity response. On the other hand, functionalized unzipped MWNTs were added to achieve a high
conductivity (0.013 S/cm) (I−V plots are shown in Figure S1,
when pure MWNTs were infused within the PU foams, it was Supporting Information). To obtain an ink composed of a MWNT−
observed that the resistance relaxation within the MWNTs rGO solution, the solution of rGO and functionalized unzipped
wrapped on the PU backbone will not be similar to the stress MWNTs was added in a 10:1 volume ratio so that the conductivity of
relaxation by the PU foams due to the difference in their the rGO solution could be increased. The mixture was stirred for 8 h
relaxation mechanisms.34 at room temperature, which was followed by 30 min of ultrasonication.

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Figure 1. Photos of (a) commercially available PU foam, (b) PU foams after embedding into the doped rGO ink, and (c) side view of the MWNT−
rGO@PU sponge piezoresistive pressure sensors.

Figure 2. Schematic of the complete procedure involved in the fabrication of the MWNT−rGO@PU piezoresistive sensor. (a) Pure PU foam after
cleaning, (b) foam dipped for the first time in doped rGO ink, (c) degassing to embed the ink into the PU skeleton, (d) PU foam after the first dip,
and (e) drying in a vacuum oven. This process (dipping followed by drying) was repeated multiple times and then (f) the dark black PU foam was
collected, and (g) ITO-coated PET sheets were connected as electrode and (h) with wires connected using silver paste. (i) Measurement under
applied strain with its electrical characteristics measured using a Keysight source/measurement unit, which was connected to a laptop, whereas (j)
shows a magnified image of the sponge under the applied strain.

The dispersion of MWNT−rGO ink was studied via the ζ potential sensors. The complete process of the fabrication of the sensor is
measurement whose value was obtained as −30.16 mV. Thus, the schematically outlined in Figure 2.
obtained MWNT−rGO ink was implemented for the coating of PU
skeleton after repeated dipping. 3. CHARACTERIZATIONS
2.4. Fabrication of Piezoresistive Pressure Sensor. Commer-
cially available polyurethane (PU) foams (Figure 1a) were sliced into 3.1. Material Characterizations. High-resolution trans-
rectangles that had dimensions of 1.3 cm × 0.8 cm and thickness of 0.5 mission electron microscopy (HRTEM) images of the ink
cm. They were washed using isopropyl alcohol (three times) and dried along with its selected area electron diffraction (SAED) images
in vacuum at 60 °C for 8 h. Thereafter, the foams were dipped in the were taken using JEOL JEM-2100 F. The scanning electron
prepared ink and degassed in a desiccator. It was then dried in a microscopy (SEM) images of the pure rGO and MWNT-added
vacuum oven for 10 h at 70 °C, and the process was repeated multiple rGO ink (Figure S2, Supporting Information) were obtained
times. Figure 1b shows a photo of the ink-soaked PU foam. To using JSM-7600F with a resolution of 1.0 nm (15 kV); an
fabricate the piezoresistive sensor, indium tin oxide (ITO)-coated accelerating voltage that ranged from 0.1 to 30 kV was used
poly(ethylene terephthalate) (PET) sheets of similar dimensions were along with a focused electron beam.
employed as electrodes (top and bottom), which were then attached 3.2. Sensor Characterization. The electromechanical
to the two rectangular faces of the PU foam using silver paste to characterization of the sensors was performed with a universal
eliminate contact resistance and to achieve a stable signal output. testing machine (Mark 10, model ESM303) with simultaneous
Figure 1c represents the final image of the piezoresistive pressure measurement of electrical characteristics recorded with a source
5187 DOI: 10.1021/acsami.7b15252
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Figure 3. HRTEM images of the rGO ink (a−c) and the MWNT-doped rGO ink (d−f) along with their SAED pattern, which was employed to
fabricate piezoresistive pressure sensors.

Figure 4. (a) Schematic diagram of the fabrication procedure of MWNT−rGO-wrapped PU foams, (b−d) SEM images of cleaned, uncoated PU
foam, and (e−g) PU foam after multiple dipping in the MWNT−rGO ink at different magnifications (50×, 200×, and 20 000×).

measure unit (Keysight, model B2902A). ESM303 is a highly 4. RESULTS AND DISCUSSION
configurable single-column force tester for tension and
To confirm the formation of rGO flakes and to observe the
compression measurements. The least detection limit of this
setup is 0.05 N, and the maximum load that can be applied distribution of the MWNTs on the rGO flakes, HRTEM was
through it is 1.5 kN. The device was placed on the chuck that is performed at various locations of the sample. The sample was
attached to the bottom of the testing machine, and the pressure prepared by diluting 10 μL of rGO ink (from 0.5 mg/mL stock
was applied in the normal direction through the top electrode. solution) in 3 mL of water in an eppendorf tube followed by 30
A vibrationless platform was used for isolation from external min of continuous ultrasonication. One drop of the solution
vibrations. was dropped through a 10 μL micropipette on a lacey copper
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Figure 5. Schematic of the MWNT−rGO flake-wrapped PU foam with the magnified image of its individual skeleton at three stages i.e., (a, d)
without pressure, (b, e) at low pressure, and (c, f) at high pressure. Here, the deformation due to applied pressure caused crack formation in rGO
flakes (white lines), leading to breakage of local conductive pathway of the carriers (red lines) at low pressure. However, the conduction pathway
became more pronounced when the MWNT−rGO@PU skeleton interfaces contacted each other.

grid, which was further dried under an IR lamp. Figure 3a−c The neatly washed PU sponge is shown in Figure 4b. The
presents the HRTEM images of the pure rGO ink that were thickness of the skeleton that forms the foam is estimated to be
collected in the dark-field mode along with their SAED approximately 100 μm, and the pores in the skeleton are
patterns. It is observed that there were wrinkles between the approximately a micrometer in size. After the deposition of
rGO flakes and the edges were folded (Figure 3a). The average rGO flakes on the PU skeleton, the surface becomes rough, as
size of the rGO flake is estimated to be more than half a can be seen in Figure 4e,f. On dipping the sponge in the
micrometer. The diffraction pattern of rGO in Figure 3b shows MWNT−rGO ink multiple times, the rGO flakes along with
12 bright spots resulting from the coupling of two hexagonal MWNTs, due to their significant affinity for the PU foam, wrap
patterns, suggesting the presence of a few highly exfoliated rGO around the uncovered region of the PU skeleton and on the
layers in rGO. On the other hand, Figure 3c confirms the already deposited flakes, covering the whole PU foam skeleton
presence of a single sixfold pattern with six bright spots. Such with rGO flakes, which is clearly visible in Figure 4g as well as
patterns were observed at several positions in the sample, which in highly magnified images provided in Figure S3, Supporting
confirms that the agglomeration of the reduced films was Information. Thus, it can be confirmed that the conductive
restricted because of the water-based additive. The results also MWNTs−rGO flakes have successfully coated the PU skeleton.
show that the prepared rGO ink retains its crystallinity in its To check the electromechanical performance of the
chemical structure. Figure 3d−f shows the HRTEM images of fabricated sensors, the devices were subjected to different
the MWNT−rGO ink, which clearly show that MWNTs are amounts of compressive strain and their resistance was
decorated on the rGO flakes in a random fashion, connecting measured (shown in Figure S4, Supporting Information). It is
flakes and each other. A few dark circular spots in the image in to be noted here that before conducting electrical measure-
Figure 3d,e were also observed, which may be due to the ments (as shown in Figures S4 and S5, Supporting
insufficient drying of the sample. The SAED pattern exhibits Information), the device was kept under 80−90% of
concentric rings instead of bright spots, which suggests that the compressive strain for an hour in the normal direction. During
crystallinity has disappeared on adding MWNTs in the rGO compression, the MWNT−rGO flakes wrapped on the PU
ink. This can happen due to the interconnection of flakes and backbone experienced maximum pressure; as a result, the PU
nanotubes, as well as due to the unzipping of the MWNTs, backbone got suppressed and interacted with the adjacent PU
shown by a circle in Figure 3f, leading to an increase in the backbones. Thus, the microcracks propagated on the MWNT−
number of layers. rGO flakes coated on the PU backbone. Although the
Figure 4a shows a schematic diagram depicting the formation of cracks is unfavorable for the device, this exercise
fabrication procedure of the MWNT−rGO@PU foam through was intentionally performed to achieve the repeatable results
multiple dips in the water-based MWNT−rGO ink. The every time. Because the direction of the applied force/pressure
magnified images (in Figure 4a) of the foam at different stages during crack formation and during measurements is identical,
suggest that the neutral skeleton of the PU foams become once the maximum number of microcracks were induced, they
wrapped with the rGO flakes until the skeleton is completely will remain unaffected during further measurements. Also, it is
covered with flakes. Finally, the original foam was turned into to be noted that the dimensions of the cracks were on the order
dark black. To confirm the deposition of rGO flakes on the of few to hundreds of microns, as depicted in Figures 4f,g and
skeleton of the PU foam, SEM images of the PU foam in its S3, Supporting Information.
pure form (Figure 4b−d) and after multiple dipping (Figure Figure 2j shows the geometry of the mechanical testing, with
4e−g) at different magnifications (50×, 200×, and 20 000×) in the compressive strain applied normal to the faces of the two
the MWNT−rGO ink were collected. It can be interpreted that electrodes that sandwich the foam. Figure 5a−f shows a
the original surface of the PU foam was smooth (Figure 4d). schematic representation of the MWNT−rGO-wrapped PU
5189 DOI: 10.1021/acsami.7b15252
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Figure 6. Electrical characteristics of the MWNT−rGO@PU sensor: (a) pressure under different values of applied strain, (b) conductivity vs strain,
(c) conductivity vs pressure, (d) relative resistance change (ΔR/Ro) vs pressure, (e) relative resistance change vs strain, and (f) the reproducibility
test of the MWNT−rGO@PU piezoresistive sensor for 5000 cycles at 50% of applied strain.

foam along with the magnified images of their individual conductivity increases with the applied strain, as shown in
skeleton at three different stages of applied pressure i.e., Figure 5. However, a very small increment was observed in the
without any applied pressure (Figure 5a,d), at a low magnitude conductivity up to 70% of strain, which may be due to the local
of pressure (Figure 5b,e), and finally at a high magnitude of conduction pathway of the charges moving along the MWNT−
pressure (Figure 5c,f). Here, the red line represents the rGO@PU conductive skeleton (Figure 5a), whereas a transition
percolation path for the charge carriers. At the rest stage, as phase was observed from 70 to 86% strain values where these
depicted in Figure 5d, the rGO-wrapped PU flakes are quite far individual covered skeleton interfaces approach each other and
apart; therefore, the propagation of the charges was permitted begin to interact physically. Because cracks form within the
along the rGO-coated PU skeleton. As the applied pressure flakes during deformation, which provide scattering sites for
magnitude was increased, as observed in Figure 5e, there mobile charges, the increment in the electrical conductivity was
appears the formation of cracks within the flakes, which causes not enough (Figure 5d,e). A rapid rise in the conductivity was
scattering of carriers at these respective sites. On reaching a measured at strain values between 86 and nearly 100%, which is
high magnitude of pressure, the individual skeleton interfaces likely due to the increased contact area between the MWNT−
interact with each other and thus an abrupt increment in the rGO@PU-coated faces of the PU skeleton, resulting in a large
electrical conductivity is observed. increment in the conductivity, as shown in Figure 5c.
The cumulative results of all of the electromechanical A further correlation of conductivity versus pressure is shown
measurements associated with the MWNT−rGO@PU pressure in Figure 6c, where conductivity is found to linearly increase
sensor are shown in Figure 6. Figure 6a shows a plot relating with the applied pressure; however, one can clearly distinguish
pressure to the compressive strain. As observed from Figure 6a, two linear regions with the abrupt transition point at an applied
initially the magnitude of the pressure slowly increases with the pressure value of 10.8 kPa, which is equivalent to 86% strain. At
applied strain; however, at approximately 86% (10.8 kPa), there the pressure range between 0 and 10.8 kPa, there is a slow
appears a sudden rise in pressure on further application of increment in the conductivity, whereas at pressure values
strain. This behavior can be interpreted on the basis of the beyond 10.8 kPa, the conductivity represents a sharp and
reaction force applied by the foam, which initially might be almost linear increase, with more than 4 times increment in its
quite low as most of the volume of the pores was occupied by magnitude, from 0.008 to 0.035 S/m at pressure values of 10.8
air. On further increasing the strain values, the PU foams and 48.8 kPa, respectively.
wrapped with the MWNT−rGO ink interact physically with The sensitivity [(ΔR/Ro)/P] measurements of the MWNT−
each other, resulting in the final pressure of 48.8 kPa associated rGO@PU piezoresistive sensor are shown in Figure 6d. It is
with nearly 100% of applied strain. Figure 6b shows the observed that the pressure-responsive behaviors of the sensors
conductivity behavior of the sensor under different magnitudes could be distinguished in three regions: positive I, negative II,
of compressive strain, which clearly demonstrates that the and negative III regions. In region I, ΔR/Ro shows a linear
5190 DOI: 10.1021/acsami.7b15252
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 Table 1. Comparative Study of the Recently Reported Piezoresistive Pressure Sensors
materials/parameters multiple steps for fabrication detection mechanism parameters ref
−1
PU foam as base material and carbon black as carbon black was stabilized using cellulose nanocrystals and chitosan microcrack-designed carbon black on PU sensitivity: 0.068 kPa (0−2.2 kPa); 0.023 25
base material and repeatedly dipped in the above prepared solution foam kPa−1 (2.2−10 kPa); 0.036 kPa−1 (above 10
kPa)
gauge factor: 2.2 (0−9%); −0.38 (9−50%); −
3.1 (above 50%)
detection limit: 91 Pa; response time: 20 ms
PU foam as base material and rGO as probe PU foam dipped in GO solution; reduced with HI and CH3COOH fractured microstructure within rGO−PU sensitivity: 0.26 kPa−1 (0−2 kPa); 0.03 kPa−1 27
to obtain rGO; hydrothermal treatment at 140 °C and foam (2.5−10 kPa); detection limit: 9 Pa
compressed (95%)
polyamic acid (PAA), polyimide (PI), and GO mixture of GO and PAA was freeze-dried and thermally reduced to high elasticity, flexibility sensitivity: 0.18 kPa−1 (0−2 kPa); 0.023 kPa−1 38
solution obtain rGO/PAA; coated with PI (above 4 kPa)
PU foam as base material and Au as a probe gold (Au) deposited using ion sputtered method on PU; channel microcrack-designed Au on PU foam sensitivity: 0.059 kPa−1 (0−4.3 kPa); 0.096 35
ACS Applied Materials & Interfaces

material cracks were designed in controlled fashion. kPa−1 (4.3−10.2 kPa); 0.122 kPa−1 (above
10.2 kPa)
gauge factor: 1.09 (0−20%); −1.37 (20−
46%); −4.43 (above 46%)
detection limit: 0.568 Pa; response time: 9 ms
PU foam as base material and MWNT−rGO ink repeated dipping of PU foam followed by 80−90% of compressive microcracks designed on MWNT-decorated sensitivity: 0.022 kPa−1 (0−2.7 kPa); 0.088 this
(our manuscript) strain after drying for microcrack formation rGO flakes kPa−1 (2.7−10 kPa); 0.034 kPa−1 (above 10 work
kPa)
gauge factor: 0.051 (0−50%); −2.13 (50−
82%); −2.3 (above 82%)
detection limit: 3.7 Pa; response time: 30 ms

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Figure 7. Real-time response (current vs time) of the MWNT−rGO@PU piezoresistive sensor for various small-scale motion monitoring
applications, such as voice detection, was studied through the throat while pronouncing different words, such as Stop, Sponge, Morning and Good
Morning (a−d); blood pulse (BP) detection through the wrist affixed through PDMS band (e) as well as the neck attached by bandage (f), and
finally, cheek bulging (g).

increase with increasing pressure (up to 2.7 kPa, 50% strain) here that the obtained performance parameters of the sensors
and exhibits a sensitivity value of 0.022 kPa−1. In this regime, it are comparable with the other reported methods, as mentioned
is highly likely that the expansion of the microcracks within the in Table 1, which are based on several substeps. Furthermore,
MWNT−rGO coating played a decisive role, causing an overall these sensors have demonstrated sensitivity values very much
increase in the resistance of the sensor.25 However, when the comparable to those of the foam-based sensors having metal
applied pressure magnitude surpassed 2.7 kPa, the conductivity sputtered on their skeleton35 in the medium pressure range.
was driven by the contacts between the faces of the MWNT− Such sensitivity can enable monitoring of tiny motions, such as
rGO-coated skeleton, resulting in a negative sensitivity of 0.088 blood pulse (BP), word recognition, cheek bulging, and so on
kPa−1 in the II regime and 0.034 kPa−1 in the III region. To (as demonstrated below). Similarly, the intensity of the signal at
achieve more insight, the gauge factor (GF) is calculated in the high strain values is very large with a noise-free signal output
three different regimes, as shown in Figure 6e, corresponding to (as shown in Figure S4, Supporting Information). This
the slope of the ΔR/R versus strain curve. Up to 50% (2.7 kPa) property enables monitoring of large-scale human movement
of applied strain, there occurs a very slight increment in the such as joint bending. Furthermore, the response time of the as-
magnitude (4.2%) of the relative resistance change [ΔR/Ro] prepared MWNT−rGO@PU-based sensor is obtained as 30
corresponding to a GF value of 0.05. Above 50% strain, the ms and the detection limit as 3.7 Pa.
relative resistance drops in a linear fashion until 86% strain The reproducibility of the MWNT−rGO@PU sensor was
(10.8 kPa) corresponding to a GF value of −2.13. Above 86% also evaluated through loading−unloading cyclic tests at 50% of
strain, it has a smooth fall till it reaches nearly 100% (48.8 kPa) compressive strain for 5000 cycles, which is shown in Figure 6f.
of strain value (GF = −2.3). Thus, it can be concluded that the The signatures that include one shoulder peak in resistance
MWNT−rGO@PU-based piezoresistive sensor is more versus time plots, as shown in Figures 6f and S4, can be
sensitive in the second and third regions with a pressure attributed to the fact that momentarily the expansion of the
regimes of 2.7−10.8 and 10.8−48.8 kPa. It is also to be noted skeleton of the foam dominates, leading to increased
5192 DOI: 10.1021/acsami.7b15252
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Figure 8. Use of the MWNT−rGO@PU piezoresistive sensor to detect finger motion. Bending at (a) 15°, (b) 45°, (c) 60°, and (d) 90°. The
response curve (I−t), which corresponds to different angular positions, has also been included.

discontinuities, which are subsequently overcome by collapsing showed a considerable change in the signature on pronouncing
of the foam structure on further application of the strain. A different words because the vocal muscles undergo different
similar kind of response behavior has been reported in the kinds of motions during pronunciation. For instance, while
literature34 too. The response signal output reflects that there is switching from saying Morning to Good Morning, there
a slight fall (0.2−0.3 kΩ) in the resistance signal prior to the appears an increment of the sharp kink in the peak feature of
saturation level due to a slight decrease in conductivity. There the current signal, i.e., from two to three, keeping the
was no further drop in the resistance value once saturation was characteristics of the rest of the current signal unchanged
achieved. The excellent reproducibility can be attributed to the (Figure 7c,d). Similarly, while uttering the word Stop, the real-
compression−resilience properties of the MWNT−rGO@PU time curve shows a sharp peak repeatedly (Figure 7a). Thus,
piezoresistive sensor (see also Figures S6 and S7 in the the significant changes among these current response curves
Supporting Information). with different motions of the throat muscles render these
sensors eligible to be employed as word-recognition devices.
5. APPLICATION AS A PRESSURE SENSOR
Furthermore, the MWNT−rGO@PU pressure sensor was
The MWNT−rGO@PU sensor has been employed in different affixed to the wrist and the neck to monitor the pulse response
applications of small-scale motion monitoring (such as pulse in real time. This can be observed in Figure 7e,f and Movie S1
monitoring at the wrist and neck, throat response while (wrist) in the Supporting Information. The current patterns in
speaking different words, cheek response while blowing) and Figure 7e,f are almost of the same shape, with the difference in
large-scale motion monitoring of finger extension and bending. the current scale possible due to the fact that the device was
5.1. Small-Scale Motion Monitoring. The capabilities of
attached with a bandage during the neck pulse response,
this flexible MWNT−rGO@PU sensor were evaluated in the
whereas a PDMS band was used for pulse measurement at the
monitoring of small-scale human activities. For the first
application, the MWNT−rGO@PU sponge was attached to wrist. Therefore, a slight tightening of the band at the wrist may
the wrist through the PDMS band and to the neck by a bandage lead to the increase in current; however, the overall response of
to observe the muscle (blood pulse or BP) motion. Figure 7a− the pulse in both the cases is similar. The insets in Figure 7e,f
d represents the current−time response to motion of the throat represent the almost similar number of peaks (7−8 peaks) that
muscles during speech, with similar current patterns observed are associated with the time-dependent current signals, within a
when repeatedly pronouncing the same word (such as “Stop”, time window of 6 s (20−26 s). This implies that the wrist and
“Sponge”, “Morning”, and “Good Morning”). This reproduci- the neck pulses measure a similar number of pulses, i.e., 80
bility indicates the stability of this fabricated sensor. Initially, a beats/min because both the places reflect a similar pulse
base-run study was carried out to receive the muscle response response. These results confirm that the MWNT−rGO@PU
without uttering any word, as shown in Figure S8, Supporting pressure sensor has an ability to detect differences in the blood
Information, indicating that it can respond to very small pulses (BP), which makes it a potential candidate for diagnostic
muscular motions. Furthermore, the current patterns recorded applications.
5193 DOI: 10.1021/acsami.7b15252
ACS Appl. Mater. Interfaces 2018, 10, 5185−5195
ACS Applied Materials & Interfaces Research Article

To demonstrate the ability of the MWNT−rGO@PU

pressure sensor to monitor respiration that takes place by the
■
*
ASSOCIATED CONTENT
S Supporting Information
expelling of air by the lungs, the fabricated sensor was attached The Supporting Information is available free of charge on the
to the cheek by a bandage and was allowed to undergo periodic ACS Publications website at DOI: 10.1021/acsami.7b15252.
blowing of air. Figure 7g shows the digital images of the sensor
I−V plot of the pure rGO as well as mixture of MWNT−
that was attached to the cheek under normal conditions and
rGO films; SEM images of the pure rGO ink and mixture
under conditions of air bulging. The current signal response
of the MWNT−rGO ink and the MWNT−rGO ink
shows a significant drop in current (from 0.95 to 0.81 mA); the
wrapped on PU foam; response curve (resistance vs
unique signature repeats throughout a time domain of 40 s for a
time) of the MWNT−rGO@PU sensor with different
healthy person. In case the person suffers from respiratory
magnitudes of the applied strain; current−voltage (I−V)
issues, there will be a change in the features of the curve, which curve of the piezoresistive sensor with strain values;
can assist in diagnosis of the illness at the initial stage. stress−strain curve of the MWNT−rGO@PU piezor-
5.2. Large-Scale Motion Monitoring. Besides small-scale esistive sensor in multiple cycles; time-dependent
motion detection, the MWNT−rGO@PU sponge pressure multicycle dynamic loading and unloading strains; base-
sensors are qualified to identify large-scale movement due to run response received from the throat muscle response
their high compressibility and piezoresistive performance under (PDF); and the MWNT−rGO@PU pressure sensor
high compressive strains. To enable measurements of finger affixed to the wrist to monitor the pulse response in real
extension and bending, the pressure sensor was mounted on time (AVI)
the proximal interphalangeal joint of the index finger with a
bandage, and the current signals were collected during the
bending−extension sequence. The digital images of the finger,
inclined at different angular positions, i.e., 15, 45, 60, and 90°,
■ AUTHOR INFORMATION
Corresponding Author
are shown in Figure 8a−d. It can be observed from the reported *E-mail: [email protected].
curves that the sensor generates different responsive signals for ORCID
different finger movements. The change in the current (ΔI = Ii Christopher R. McNeill: 0000-0001-5221-878X
− If, where Ii and If are the current values at extension and Dipti Gupta: 0000-0003-3252-3407
bending, respectively) depends upon the degree of bending Notes
with average values of 0.04 mA (15°), 0.2 mA (45°), 0.67 mA The authors declare no competing financial interest.

■
(60°), and 0.8 mA (90°) recorded for the different movements.
Therefore, the larger the degree of bending, the higher the peak ACKNOWLEDGMENTS
intensity. This could be attributed to the mild compression that The authors would like to acknowledge the Department of
was caused by the small angular motion, which led to the Science and Technology (DST), India (Grant Nos. DS.TSG/
disconnection of microcracks, and to the larger angular motion AMT/2015/617/G and IUSSTF/NIBIB_DST/ABPM/ 2014/
resulting in interaction across a larger area of the flakes that EOI_34) and IITB-Monash Research Academy for providing
were wrapped on the PU skeleton. Thus, it has been shown that funding to carry out this research. The authors are thankful to
MWNT−rGO@PU sensors can be applied to distinguish Dr. Mark Thompson (CEO Talga Company) and Dr. B. Weber
between different orientations of finger movements. (BYK Additive and Instruments) for providing us with the
additives. The authors also thank the Center for Excellence in
6. CONCLUSIONS Nanoelectronics (CEN), the Sophisticated Analytical Instru-
In summary, we have demonstrated a simple, inexpensive, one- ment Facility (SAIF), the Department of Metallurgical
step technique for the fabrication of a flexible and versatile Engineering and Materials Science (MEMS) at the Indian
pressure sensor using a MWNT-doped rGO ink that can be Institute of Technology Bombay (IIT Bombay), Mumbai, for
used in human−machine interfacing applications. The providing various facilities for device fabrication and character-
challenge of the agglomeration of rGO flakes was resolved ization.
using a water-based additive, which resulted in a highly
dispersive rGO ink that can be employed directly in the
fabrication of the sensor. The incorporation of functionalized
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