Research Article

www.acsami.org

Reduced Graphene Oxide-Containing Smart Hydrogels with

Excellent Electro-Response and Mechanical Properties for Soft
Actuators
Chao Yang,† Zhuang Liu,*,† Chen Chen,† Kun Shi,† Lei Zhang,† Xiao-Jie Ju,†,‡ Wei Wang,†,‡ Rui Xie,†,‡
and Liang-Yin Chu*,†,‡,§
†
School of Chemical Engineering, Sichuan University, Chengdu, Sichuan 610065, P. R. China
‡
State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, Sichuan 610065, P. R. China
§
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*
S Supporting Information

ABSTRACT: A novel reduced graphene oxide/poly(2-acrylamido-2-methylpropanesulfonic acid-co-acrylamide) (rGO/poly-

(AMPS-co-AAm)) nanocomposite hydrogel that possesses excellent electro-response and mechanical properties has been
successfully developed. The rGO nanosheets that homogeneously dispersed in the hydrogels could provide prominent
conductive platforms for promoting the ion transport inside the hydrogels to generate significant osmotic pressure between the
outside and inside of such nanocomposite hydrogels. Thus, the electro-responsive rate and degree of the hydrogel for both
deswelling and bending performances become rapid and remarkable. Moreover, the enhanced mechanical properties including
both the tensile strength and compressive strength of rGO/poly(AMPS-co-AAm) hydrogels are improved by the hydrogen-bond
interactions between the rGO nanosheets and polymer chains, which could dissipate the strain energy in the polymeric networks
of the hydrogels. The proposed rGO/poly(AMPS-co-AAm) nanocomposite hydrogels with improved mechanical properties
exhibit rapid, significant, and reversible electro-response, which show great potential for developing remotely controlled electro-
responsive hydrogel systems, such as smart actuators and soft manipulators.
KEYWORDS: reduced graphene oxide, stimuli-responsive materials, hydrogels, electro-response, actuators

■ INTRODUCTION
Smart hydrogels have drawn considerable attention for myriad
applications including optical systems,1 chemical valves,2
vehicles for drug delivery,3−5 biomimetic engineering,6−8 and
tissue engineering.9−11 It is attributed to their changeable
volume or physical/chemical properties responding to environ-
mental stimuli like temperature,12−15 pH,16−18 electric
field,19−22 humidity,23−25 light,26−28 special ions, or mole-
cules.29−32 Because the electric stimuli can be remotely and
facilely controlled with adjustable direction and strength, the
electro-responsive hydrogels have attracted considerable
interest. The hydrogels composed of polyelectrolyte, possessing
electro-responsive swelling/shrinking or bending/unbending,
are capable to accomplish the conversion of electric energy to
mechanical energy for soft actuators.33,34 Typically, the most
popular electro-responsive hydrogel is constituted of poly(2-
acrylamido-2-methylpropanesulfonic acid) (PAMPS) polymer,
which is polymerized by the strong acidic monomer, 2-
acrylamido-2-methylpropanesulfonic acid (AMPS). Such a
monomer can completely ionize in aqueous solution over a
broad pH range from 2 to 12, resulting in the good electro-
responsive property of PAMPS hydrogel, which is not
conspicuously affected by pH. Thus, compared with other
weak electrolyte hydrogels like poly(acrylic acid)-based hydro-
gels whose responsive properties are influenced by environ-
mental pH values, the PAMPS hydrogels show great application
Received: February 5, 2017
Accepted: April 20, 2017
Published: April 20, 2017

© 2017 American Chemical Society 15758 DOI: 10.1021/acsami.7b01710

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potentials. For example, because of their electro-response,
PAMPS hydrogels have been extensively applied for fabricating
soft biomimetic actuators (e.g., artificial muscle,35,36 crawler,20
“swimming” device,37,38 and robotic hand).39 In the application
of the hydrogels for soft actuators, the responsiveness and
mechanical properties are two critical characteristics. To
achieve the versatility of these hydrogels, fast and significant
responsiveness and excellent mechanical properties are desired
in most cases.40−45 For example, these characteristics would
contribute a conspicuous and rapid feedback in response to
environmental stimuli, whereas the good deformability and
extensibility would withstand the extraneous forces. Actually,
conventional PAMPS polymeric hydrogels cross-linked by
small molecules exhibit poor mechanical properties originating
from the irregular distribution of the cross-linking points and
the widespread distribution of the cross-linked chain lengths,
which seriously restrict the application scope of such hydro-
gels.40 Meanwhile, the electro-responsive properties of PAMPS
hydrogels are still coveted to be further enhanced for expansive
uses. Thus, the development of PAMPS-based hydrogels
possessing rapid and significant electro-response as well as
excellent mechanical properties has a great significance in both
science and technology.
So far, the electro-responsive property of PAMPS hydrogels
can be improved by the following strategies. One strategy is
fabricating the PAMPS hydrogels with macroporous structure
to improve the ionic transport in the polymer network. For
example, Lin and co-workers have fabricated PAMPS hydrogels
with macroporous structure employing polyethylene glycol
6000 (PEG6000) molecules as pore-forming agents.46 When
the hydrogels with sizes of 20 mm × 4 mm × 2 mm are
immersed in 0.05 M NaCl solution under a voltage of 30 V, the
bending curvature of the PAMPS hydrogels with macroporous
structure introduced by PEG6000 could increase from 0.0297
mm−1 to 0.0454 mm−1 within 5 min. Compared with the
equilibrium bending curvature of control PAMPS hydrogels
without the introduction of PEG6000 being 0.0401 mm−1, that
of the macroporous PAMPS hydrogels at equilibrium state only
increases to 0.0489 mm−1. Although the electro-responsive
property of PAMPS hydrogels can be improved to a certain
extent by forming the macroporous structure, the mechanical
properties of the hydrogels tend to weaken because of the
macropores in the polymeric network.40,47 Alternatively, adding
some electro-active components such as polypyrrole (PPy) and
polyaniline (PANI) can also improve the electro-responsive
property of PAMPS hydrogels.48,49 For instance, Wu and co-
workers have introduced PANI into PAMPS-based hydrogels to
form interpenetrating polymer networks (IPN).49 Such PANI-
containing IPN hydrogel with size of 20 mm × 4 mm × 2 mm
reaches its equilibrium bending curvature more rapidly in a 0.2
M NaCl solution with an applied electric field of 25 V. The
required time decreases from 20 to 13 min compared with that
of normal PAMPS hydrogels. Moreover, the interpenetrating
polymer networks enable the hydrogels to improve the
mechanical properties. Gangopadhyay and co-workers have
fabricated an electrically conducting semi-IPN PAMPS hydro-
gel with linear conducting PANI entrapped in the polymeric
network.50 Compared with that of normal PAMPS hydrogel,
the compressive stress of the semi-IPN one increases from 0.3
to 0.75 MPa. In addition, the tensile stress increases from 0.012
to 0.014 MPa, but the tensile fracture strain only increases from
40% to 92%. The semi-IPN PAMPS hydrogels could achieve an
increase in compressive strength, while the enhancement of
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tensile strength is limited, which may restrict their practical
applications for soft actuators. Thus, the preparation of
PAMPS-based hydrogels with excellent electro-responsiveness
and mechanical properties, especially the tensile strength, is still
a dilemma.
Here, we report a novel nanocomposite PAMPS-based
hydrogel with excellent electro-response and mechanical
properties by introducing reduced graphene oxide (rGO)
nanosheets into poly(2-acrylamido-2-methylpropanesulfonic
acid-co-acrylamide) (poly(AMPS-co-AAm)) hydrogel. Com-
pared with the normal PAMPS hydrogels, the rGO/poly-
(AMPS-co-AAm) nanocomposite hydrogels exhibit rapid and
significant response to an electric stimulus because of the
excellent electronic conductivity of rGO nanosheets enhancing
the ion transport in the polymeric network. It has been
reported that the rGO nanosheets exhibit excellent electronic
conductivity;51−57 thus, they can provide electric platforms to
promote the ion transport in the rGO/poly(AMPS-co-AAm)
nanocomposite hydrogels under electric field. The deformation
behaviors of electro-responsive hydrogels can be explained by
Flory’s theory of the osmotic pressure.33 The proposed
mechanism on the improvement of electro-responsive property
in this study is different from that reported in the previous
works implementing incorporation of graphene oxide (GO)
nanosheets into electro-responsive poly(acrylic acid) and
polyacrylamide-co-poly(acrylic acid) hydrogels,58,59 in which
the electro-responsive performances are enhanced because of
the carboxyl groups of GO nanosheets in the alkalescent
aqueous solution. When a DC electric field is applied, the
electrons in the electrostatic double layer of the GO nanosheets
are polarized, and thus a secondary electric field that combines
with and strengthens the first field is generated, which
contributes to the improvement of the bending actuation
performance.58 However, in our rGO/poly(AMPS-co-AAm)
nanocomposite hydrogel networks, with the assistance of rGO
nanosheets as conductive platforms, the ions directionally move
out to quickly generate a remarkable osmotic pressure due to
the strong acidic group of the propanesulfonic acid in the
networks. The nanocomposite hydrogels are proposed with
controllable and reversible electro-induced deswelling and
bending behaviors under cyclic “on/off” electrical fields.
Meanwhile, the tensile strength and compressive strength are
both increased with addition of rGO nanosheets because of the
composite structure of polymer matrix and rGO nanosheets,
which is beneficial for dissipating energy. The proposed rGO/
poly(AMPS-co-AAm) nanocomposite hydrogels possess ex-
cellent electro-responsiveness and mechanical properties, so
that they have great prospects for the applications of remotely
controllable intelligent systems, like soft actuators, robots, and
artificial muscles.
■ EXPERIMENTAL SECTION
Materials. 2-Acrylamido-2-methylpropanesulfonic acid (AMPS)
from Sigma-Aldrich and potassium persulfate (KPS, K2S2O8),
acrylamide (AAm), N,N′-methylenebis(acrylamide) (MBA), sodium
chloride (NaCl), hydrazine hydrate, and ammonia solution from
Chengdu Kelong Chemical Reagents were used as received without
further purification. Raw graphite (325 mesh) purchased from XF
NANO Ltd. was used to synthesize graphene oxide (GO) via the
modified method of Hummers.60 Deionized water from a water
purification system (Milli-Q Plus, Millipore) was used.
Preparation of rGO/Poly(AMPS-co-AAm) Nanocomposite
Hydrogels. The nanocomposite hydrogels were synthesized using
thermal-induced polymerization method with AMPS and AAm as
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Figure 1. Schematic illustration of fabrication process and structure of the proposed rGO/poly(AMPS-co-AAm) nanocomposite hydrogels. (a,b)
The polymerization of hydrogel is simultaneous with the reduction of graphene oxide. (c) The rGO/poly(AMPS-co-AAm) nanocomposite hydrogels
are chemically cross-linked by MBA, and the hydrogen-bond interactions between rGO nanosheets and polymer chains result in the physical cross-
linking.
monomers, MBA as chemical cross-linking agent, GO nanosheets as
additives, and KPS as initiator. Typically, AMPS (0.7 M), AAm (0.3
M), MBA (0.05 M), and KPS (0.01 M) were dissolved in the GO
suspension (5 mL). Next, hydrazine hydrate and ammonia solution
were added to the reaction solution. The weight of hydrazine was
about 70% to that of GO, and the volume ratio of hydrazine solution
to ammonia solution was about 1:7. After the reaction solution was
vigorously stirred and subjected to ultrasonic treatment, the solution
was put into a water bath for simultaneous polymerization and
reduction at 65 °C for 8 h. Subsequently, the resulting product was
kept at 90 °C for 1 h for further reduction of GO. To study the
influences of the rGO content on the electro-responsiveness and
mechanical properties, a series of rGO/poly(AMPS-co-AAm) nano-
composite hydrogels were prepared containing different rGO contents
according the GO concentration in the reaction solution, which was
typically 0.2, 0.5, and 1.0 mg·mL−1. The as-prepared rGO/poly-
(AMPS-co-AAm) nanocomposite hydrogels were labeled as “rGO-x”,
in which “x” represents the mass concentration of GO (mg·mL−1). For
comparison, poly(AMPS-co-AAm) hydrogels (labeled as “blank gel”)
were also prepared by the similar method but without addition of GO
nanosheets. After the hydrogels were polymerized and reduced, they
were thoroughly purified with excessive water.
SEM and TEM Characterizations and Raman Spectra of
Hydrogels. The microstructures of the proposed hydrogels were
observed by field emission scanning electron microscope (FESEM,
JSM-7500F, JEOL). The hydrogel samples were treated by freeze-
drying method for SEM observation. The dispersion morphology of
rGO nanosheets in the nanocomposite hydrogel was studied by
transmission electron microscope (TEM, Tecnai G2 F20 S-TWIN).
To prepare samples for TEM observation, the ultrathin lamella of the
hydrogel was first cut with cryosection system (Leica FC6) and then
collected on copper grids and subsequently dried at room temperature.
Raman spectra were obtained from a Raman microscope (Horiba
Jobin Yvon LabRAM HR). The experimental samples were rGO
power and rGO-0.5 hydrogel, which were measured after lyophiliza-
tion. A diode laser operated at 633 nm was used for excitation.
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Mechanical Property Tests. Measurements of the mechanical
properties of the as-prepared hydrogels were performed with a testing
machine (EZ-LX, Shimadzu) at 25 °C. For the tensile tests, the rod-
like samples (the diameter is 4.3 mm, the length is 30 mm and the
gauge length is 10 mm) were stretched under a constant rate of 100
mm/min. For the compressive tests, cylindrical samples with a
diameter of 12.6 mm and a height of 10 mm were put between the
self-leveling plates. The compressed rate on the samples was 100 mm/
min.
Electro-Induced Deswelling Behavior Tests. The electro-
induced deswelling behaviors of hydrogels were investigated by
monitoring the weight change upon exposure to a DC electric voltage
of 10 V using a power supply. The equipment illustrated in Figure S1
was used to study the shrinking behavior of the hydrogel. Fully swollen
hydrogels with the size of 10.0 mm × 5.0 mm × 5.0 mm were glued
with two carbon electrodes, which were connected to a DC power
supply. The contact area is 10.0 mm × 5.0 mm. Water would be
released from the hydrogels under the DC electric voltage. Weight
measurements of the hydrogels were achieved by an electronic balance
at various time intervals. The deswelling behaviors of the hydrogels
were evaluated by the weight change of the hydrogels. The weight
change percentage could be calculated as follows:
weight change percentage (%) = Wt /W0 × 100% (1)
where Wt is the measured hydrogel weight at time t under electric
field, W0 is the hydrogel weight at t = 0 s (fully swollen state). To
investigate the reversibility of the deswelling/swelling properties of
such hydrogels, the rGO/poly(AMPS-co-AAm) nanocomposite hydro-
gels were alternately exposed to an electric field (10 V). The electric
field was turned on for 2 min to reach the full deswelling of the
hydrogel. Then, the hydrogels were immersed in water for 6 min
without an electric stimulus.
In addition, the electrical conductivity of nanocomposite hydrogels
before and after the reduction of GO have been measured using a
source meter (Model 2401, Keithley). The electrical conductivity (σ)
was calculated using the following two equations:
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ρ = R s × l(Ω. m) (2) images show the hydrogels are homogeneously fabricated by

our strategy and the color of the hydrogel becomes darker with
σ = 1/ρ(S/m) (3) increasing the rGO content (Figure 2a), compared with the
where ρ is the bulk resistivity of the hydrogels, Rs is the sheet
resistance, and l is the thickness of the sample between two probes.
Electro-Induced Bending Behavior Tests. The hydrogel
samples of blank gel and rGO-0.5 hydrogel were used to investigate
the bending behaviors. The size of both hydrogel samples was 20.0
mm × 2.0 mm × 1.0 mm (length × width × thickness). The
methylene blue was used to dye the blank gel samples for easy
observation. The equipment illustrated in Figure S2 was used to study
the bending behaviors of hydrogel. Two carbon electrodes in NaCl
solution (0.01 M) were parallelly placed with a distance of 44 mm,
which were connected to a DC power supply to form a horizontal
electric field. Furthermore, the hydrogel strips were vertically put in
the solution and placed centrally between the two electrodes, with 20.0
mm × 2.0 mm side facing the electrodes. The top of the hydrogel strip
was fixed by a clamp and ca. 15.0 mm in length was immersed in the
solution with a 10 V supply voltage. We used a camera (E-PL5,
Olympus) to record the bending behaviors of the hydrogel samples
within 2 min.
Applications of Hydrogels as Soft Actuators. The size of
hydrogel strips was 25.0 mm × 3.0 mm × 0.5 mm (length × width ×
thickness). Using the same equipment illustrated in Figure S2, the
hydrogel strip was immersed in 0.01 M NaCl solution with a length of
17.0 mm and was used to act as a “hydrogel cantilever”. The applied
electric voltage was 10 V. The target objects were polydimethylsilox-
ane (PDMS) blocks with different masses (0.2 or 0.4 g). The whole
actuating behaviors of these hydrogels were recorded with a camera.
Then, rectangular hydrogels with sizes of 35.0 mm × 10.0 mm × 0.5
mm (length × width × thickness) were tied to a string by magnetic
sheets to perform as a “hydrogel gripper”. The schematic diagram of Figure 2. Optical (a) and SEM (b) images of hydrogels with different
the equipment of the hydrogels gripping motion was shown in Figure contents of rGO. (b1) blank gel, (b2) rGO-0.2, (b3) rGO-0.5, and
S3. The distance of the two parallel carbon electrodes was 34 mm. A (b4) rGO-1.0. Scale bars in SEM images are 100 μm.
substrate was put in the center of the two electrodes to form a
platform. The PDMS strip with length of 15 mm as target object for
gripping was put on the platform. The gripping behaviors of hydrogels nanocomposite hydrogel that prepared by directly doping rGO
were recorded with a camera. The applied electric voltage was 30 V.

■
RESULTS AND DISCUSSION
Fabrication Strategy. The fabrication strategy of the
proposed nanocomposite hydrogels is illustrated in Figure 1.
First, the monomer solution containing AMPS, AAm, MBA,
and GO nanosheets is treated by an ultrasound for 10 min to
make GO nanosheets homogeneously dispersed in the solution
(Figure 1a). Then, the polymerization is initiated by KPS. The
reduction of the GO nanosheets happens at the same time to
avoid of the aggregation problem of rGO nanosheets in the
hydrogel networks, which is further reduced again (Figure 1b).
For the rGO-containing poly(AMPS-co-AAm) hydrogel, the
AAm groups are added to make the polymer chains soft.21 The
hydrogel network is chemically cross-linked via the covalent
bonds created by MBA molecules (Figure 1b). Additionally, the
residual oxygen-containing groups on the edge of rGO
nanosheets such as hydroxyl and carbonyl enable to form
hydrogen-bond interactions with the groups of poly(AMPS-co-
AAm) chains (Figure 1c), which can physically cross-link the
copolymer chains, thus increasing the mechanical properties of
the nanocomposite hydrogels via dissipating the uneven force.61
The rGO nanosheets exhibit excellent electronic conductivity
and thus provide electric platforms to promote the ion
transport in the hydrogel under electric field.51−57 As a result,
the rGO/poly(AMPS-co-AAm) hydrogels are expected to
exhibit good electro-responsiveness.
Optical and Morphological Analyses of rGO/Poly-
(AMPS-co-AAm) Nanocomposite Hydrogels. Optical
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nanosheets (Figure S4). Typical TEM images show the
homodispersed distribution of rGO nanosheets in the rGO/
poly(AMPS-co-AAm) hydrogel prepared by our strategy
(Figure S5). The SEM images show the internal network
structures of the hydrogel samples with different contents of
rGO (Figure 2b). The porous structures of the hydrogels are
caused by the ice crystals, which act as the pore-forming
templates during the lyophilization. The network structures
become denser and more compact with an increase in the rGO
content because of the increased physical cross-linking caused
by the enhancement of interaction between rGO nanosheets
and polymeric networks. The results indicate that the rGO
content remarkably influences the internal network structures
of hydrogels by forming physical cross-linking between rGO
nanosheets and polymeric chains.
Further, as shown in the Raman spectra (Figure 3), the G-
band and D-band of rGO nanosheets (lower) and rGO-0.5
hydrogel (upper) are presented. Compared to the G-band and
D-band positions of rGO nanosheets, the rGO-0.5 hydrogel
shows a positive shift of D-band while a negative shift of G-
band. The G-band negatively shifts from 1610 to 1606 cm−1,
and the D-band of rGO-0.5 hydrogel positively shifts from 1329
to 1338 cm−1. The results imply the interaction between the
rGO and polymeric chains.62,63
Mechanical Properties of rGO/Poly(AMPS-co-AAm)
Nanocomposite Hydrogels. The mechanical properties of
the nanocomposite hydrogels are measured in relative shrinking
states rather than fully swollen states, because the nano-
composite hydrogels are ususally considered to apply for
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Figure 3. Raman spectra of rGO powder and the rGO-0.5 hydrogel.
applications with stimuli-induced bending, which is caused by
the asymmetric shrinking of the hydrogel due to the osmotic
pressure difference induced by electric-field-driven ion motion.
Compared with blank gel samples, the rGO/poly(AMPS-co-
AAm) nanocomposite hydrogels exhibit excellent mechanical
properties on both tensile strength and compressive strength.
The blank gel is easy to be broken by elongating and
compressing (Figure 4a1, Supplementary Movie S1). Excitingly,
the composite hydrogel containing rGO, such as rGO-0.5
sample, displays a high performance in tensile strength. It can
be knotted and then stretched without damage (Figure 4a2,
Supplementary Movie S2). Under the same compression, the
composite hydrogel is stronger than the blank hydrogel to
withstand the high deformation (Figure 4b, Supplementary
Movie S3). Upon removal of the compression, the rGO-0.5
hydrogel quickly recovers its original shape. The blank gel is
broken at the compressive stress of 0.4 MPa (Figure 4c). By
introducing rGO nanosheets in the network of rGO-0.5
hydrogel, its compressive stress at broken point is increased
to 1.4 MPa. Furthermore, the mechanical tensile stress tests of
hydrogels with different contents of rGO are performed by
using a universal testing machine. The stress−strain curves of
blank gel, rGO-0.2, rGO-0.5, and rGO-1.0 hydrogels are shown
in Figure 4d. Both the fracture stress and strain are increased
with increasing the rGO content due to the incremental
physical cross-linking. As a comparison, the tensile mechanical
properties of fully swollen rGO-0.5 hydrogel is decreased
(Figure S6). As shown in Figure 4e, all the fracture stresses of
the rGO/poly(AMPS-co-AAm) nanocomposite hydrogels are
higher than that of the blank gel sample. The fracture stress of
rGO-1.0 hydrogel is 96.68 kPa, which is 4 times larger than that
of the blank gel. The tensile fracture strains of the hydrogels
also increase gradually with increasing rGO content (Figure 4f).
The fracture tensile strain of rGO-1.0 hydrogel reaches
297.93%. The addition of rGO nanosheets makes the
nanocomposite hydrogels more elastic, and the elastic modulus
of the hydrogels will increase as the rGO content increases
(Figure S7), which may imply the physical cross-linking
mechanism between the rGO and the matrix. The results
confirm that the hydrogen-bond interactions between the rGO
nanosheets and poly(AMPS-co-AAm) chains are expected to
transfer load between the polymer chains and rGO nanosheets,
resulting in the enhancement of mechanical properties.
Additionally, the rGO nanosheets can twirl parallel to the
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strain axis in the polymeric network during stretching process,
causing the dissipation of strain.64,65
Electro-Responsive Properties of rGO/Poly(AMPS-co-
AAm) Nanocomposite Hydrogels. When the rGO/poly-
(AMPS-co-AAm) nanocomposite hydrogels are placed in
contact with both electrodes under electric fields (as illustrated
in Figure S1), the shrinking deformation of the hydrogels
occurs. The electric field not only produces the motion of free
ions that causes the electro-osmosis of water which is due to the
asymmetrical distribution of ions between the interior and
exterior of the hydrogel but also engenders a force on the
negatively charged sulfonic acid groups in the polymer network.
The stress gradient makes the hydrogel shrink.33,66−68 The
electro-induced deswelling behaviors of hydrogels containing
different contents of rGO are investigated by monitoring the
weight loss under an electric field with DC voltage of 10 V. The
water is released from the hydrogel matrix, which is monitored
at various time intervals. The reduction effect of GO mainly
depends on treatment temperature,69 so the resulting mixture
has been kept at 90 °C for 1 h for further reduction of GO. The
reduction of GO can significantly increase the electrical
conductivity of the nanocomposite hydrogels (Figure S8),
thus providing better electric platforms to promote the ion
transport in the nanocomposite hydrogels under electric field.
Therefore, the electro-responsive property of rGO/poly-
(AMPS-co-AAm) nanocomposite hydrogels could be improved
by further reducing the rGO nanosheets (Figure S9). As shown
in Figure 5a, the rGO content in the network affects the
deswelling behaviors of hydrogels under voltage of 10 V. There
is an improvement of the electro-induced deswelling property
as the content of rGO increases from 0 to 1.0 mg mL−1. For
example, the rGO-1.0 hydrogel displays a relatively rapid
deswelling, and the weight loss ratio is approximately 71%
within 5 min. However, the weight loss ratio of blank gel only
achieved to be ∼35% within 5 min. It is thus confirmed that the
rGO/poly(AMPS-co-AAm) nanocomposite hydrogels deswell
faster than the blank gel due to the rGO nanosheets in the
networks, which promote the ion transport in the hydrogel with
DC voltage of 10 V. When the applied voltage increases from 5,
10 V to 15 V, the rGO-0.5 hydrogel exhibits faster and more
significant deswelling behavior (Figure 5b). Moreover, to
investigate the reversibility and repeatability of the swelling/
shrinking behaviors, the rGO-0.5 hydrogels are alternately
exposed to an electric field (10 V). The electric field with DC
voltage of 10 V is applied to the hydrogels for 2 min. After
removing the electric field, the hydrogels are put in water to
swell for 6 min. As shown in Figure 6, when applying the
electric field for 2 min, hydrogels shrink to 58−68% of original
weight; when removing the electric field and then immersing
the shrunken hydrogels in water for 6 min, the rGO-0.5
hydrogels can reswell. The results confirm the excellent
reversible electro-induced swelling/shrinking properties of
such nanocomposite hydrogels.
Under the noncontact electric field in an electrolyte solution
(Figure S2), the rGO/poly(AMPS-co-AAm) hydrogel strips
show bending deformation. Because the transport of mobile
ions under the electric field causes osmotic pressure difference
between the exterior and interior of the hydrogels, which drives
the bending of rGO/poly(AMPS-co-AAm) hydrogels toward
the cathode. When the PAMPS-based hydrogels are loaded
with noncontact electric field in an electrolyte solution such as
NaCl, the free ions in the solution will transport to the counter-
electrodes. However, the cross-linked polymer networks will
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Figure 4. Mechanical properties of hydrogels. (a,b) Tensile test (a) and compressive test (b) of blank gel and rGO-0.5 hydrogel. (c,d) Compressive
stress−strain curves (c) and tensile stress−strain curves (d) for blank gel and rGO-containing hydrogels. (e,f) Effects of rGO concentration on the
tensile fracture stress (e) and tensile fracture strain (f) of hydrogels.
prevent the transport of the sulfonic groups, only counterions
of the sulfonic groups are mobile and can transport to the
counter electrodes. Thus, an ionic concentration gradient will
be created along the direction of the electric fields because of
the ion motions, which leads to the osmotic pressure difference
inside the hydrogels.21,68 The osmotic pressure of the hydrogel
side facing the anode is greater than that of the opposite side
facing the cathode, so the hydrogel will bend to the cathode
side.21 To investigate the electro-induced bending behaviors of
the hydrogels containing different rGO contents, hydrogel
samples are immersed in electrolyte and put centrally between
two electrodes (Figure S2). The curvature value is used to
evaluate the bending behaviors of hydrogels. Compared with
the blank gel (Figure 7a), the rGO-0.5 hydrogel bends faster
and more significant (Figure 7b, Supplementary Movie S4). As
shown in Figure 7c, both the rate and degree of the bending
deformation are increased as the rGO content increases. The
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curvature value of the rGO-1.0 hydrogel reaches 0.088 mm−1,
whereas that of the blank gel is only 0.05 mm−1. The results
indicate that the incorporation with rGO nanosheets could
improve the electro-responsiveness including both bending rate
and bending degree of hydrogels.
Demonstrations of rGO/Poly(AMPS-co-AAm) Nano-
composite Hydrogels as Actuators. The rGO/poly(AMPS-
co-AAm) nanocomposite hydrogels exhibit reversible bending
behaviors in electrolyte solutions, so they are highly attractive
and promising to be used as soft actuators by alternately
applying electric field. To demonstrate the applications, the
hydrogels are designed as “soft cantilevers” and “soft grippers”
on the basis of their electro-induced bending behaviors.
The blank gel and rGO-0.5 hydrogel are first cut into strips
and then used as “hydrogel cantilevers”. The hydrogel strips are
vertically immersed in the solution with the top fixed, which are
placed centrally between the two electrodes. PDMS blocks (0.2
DOI: 10.1021/acsami.7b01710
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ACS Applied Materials & Interfaces
Figure 5. (a) Effect of rGO concentration on the deswelling behaviors
of hydrogels with different rGO contents with an applied voltage of 10
V. (b) Effect of applied voltage on the deswelling behaviors of rGO-0.5
hydrogels.
Figure 6. Reversible deswelling/swelling behaviors of rGO-0.5
hydrogel under cyclic “on/off” electric fields (10 V; on: 2 min; off:
6 min).
or 0.4 g) are used as target objects for lifting. The lifting
behaviors of blank gel and rGO-0.5 hydrogel for lifting the 0.2 g
PDMS blocks are shown in Figure 8a,b, respectively
(Supplementary Movie S5). By applying an electric voltage of
10 V, both blank gel and rGO-0.5 hydrogel can bend toward
the cathode side and lift the PDMS block. Compared with the
blank gel, the rGO-0.5 hydrogel could lift the block (0.2 g)
faster and higher. When lifting a heavier block (0.4 g), the blank
gel could not afford an efficient driving force to achieve the
lifting of the block (Figure 8c). While the rGO-0.5 hydrogel
could lift the 0.4 g heavy load successfully (Figure 8d,
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Research Article
Figure 7. Effect of rGO content on the bending behaviors of rGO/
poly(AMPS-co-AAm) composite hydrogels with an applied voltage of
10 V. (a,b) Optical photographs of the electro-responsive bending
behaviors of blank gel (a) and rGO-0.5 hydrogel (b). (c) Electro-
responsive change of the curvature of hydrogels with different rGO
contents.
Supplementary Movie S6). By taking into account the buoyant
force, the real output force of the nanocomposite hydrogel
upon electro-responsive bending is calculated as ca. 0.38 mN.
The results show the actuating performances of rGO-
containing hydrogels are better than that of the blank gel due
to the incorporation of rGO nanosheets in the hydrogels
improves both electro-responsive property and mechanical
properties.
The blank gel and rGO-0.5 hydrogel are also used as
“hydrogel grippers”. First, the hydrogels are cut into rectangles
and then connected to a string by using magnetic sheets. The
“hydrogel gripper” is hung between two parallel carbon
electrodes to pick up the target object, remotely controlled
by applying an electric field (Figure S3). The length of the
target object is 15 mm. As shown in Figure 8e, under the
electric voltage of 30 V, the blank gel still could not generate
enough bending deformation to capture the target object within
30 s. However, the rGO-0.5 hydrogel could sufficiently bend to
pick up the target object within only 12 s (Figure 8f,
Supplementary Movie S7).
■
CONCLUSIONS
In summary, rGO/poly(AMPS-co-AAm) nanocomposite hy-
drogels with excellent electro-response and mechanical proper-
ties have been developed by a two-step reduction method to
avoid the aggregation of rGO nanosheets in the hydrogel
networks. The incorporation of rGO nanosheets could
physically cross-link the poly(AMPS-co-AAm) chains, resulting
in effective dissipation of strain and transfer of load between the
polymer networks and the rGO nanosheets. The mechanical
properties of the nanocomposite hydrogels are significantly
improved on both tensile strength and compressive strength.
The excellent electronic conductivity of rGO nanosheets
DOI: 10.1021/acsami.7b01710
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ACS Applied Materials & Interfaces
Figure 8. Applications of hydrogels as “hydrogel cantilevers” (a−d) and “hydrogel grippers” (e,f). (a,b) The lifting behaviors of blank gel (a) and
rGO-0.5 hydrogel (b) cantilevers for lifting PDMS block with weight of 0.2 g. (c,d) The lifting behaviors of blank gel (c) and rGO-0.5 hydrogel(d)
for lifting PDMS block with weight of 0.4 g. (e,f) The gripping behaviors of blank gel (e) and rGO-0.5 hydrogel (f) grippers for gripping a target
object with length of 15 mm.
enables to promote the ion transport in the hydrogels, thus
causing improved electro-responsive properties including both
deswelling/swelling and bending/unbending performances.
The rGO/poly(AMPS-co-AAm) nanocomposite hydrogels
exhibit repeatable and reversible responsive deformation by
cyclically applying electric fields. The responsive rate and
degree are increased with increasing the rGO content of
hydrogels. Based on the electro-induced bending property, the
proposed nanocomposite hydrogels are capable to be
developed as soft robots like cantilevers and grippers. Such
nanocomposite hydrogel systems show great potential in
myriad applications for remote manipulation and trans-
portation.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.7b01710.
Schematic illustration of the device for studying the
electro-induced deswelling behaviors of hydrogels;
schematic illustration of the device for studying the
electro-induced bending behaviors of hydrogels; sche-
matic illustration of the device to perform a “hydrogel
gripper”; optical image of nanocomposite hydrogel
15765
Research Article
prepared by directly doping rGO nanosheets; TEM
image of rGO-0.5 hydrogel; tensile stress−strain curve of
the fully swollen rGO-0.5 hydrogel; effect of rGO
concentration on the elastic modulus of hydrogel; effect
of the reduction of GO on the electrical conductivity of
hydrogel; effect of the reduction of GO on the electro-
induced deswelling behavior of hydrogel (PDF)
Movie S1: tensile test performed on the blank gel (AVI)
Movie S2: tensile test performed on the rGO-0.5
hydrogel (AVI)
Movie S3: compressive test performed on the blank gel
and rGO-0.5 hydrogel (AVI)
Movie S4: electro-responsive bending behaviors of blank
gel and rGO-0.5 hydrogel (AVI)
Movie S5: lifting behaviors of blank gel and rGO-0.5
hydrogel for the load with weight of 0.2 g (AVI)
Movie S6: lifting behaviors of blank gel and rGO-0.5
hydrogel for the load with weight of 0.4 g (AVI)
Movie S7: gripping behaviors of blank gel and rGO-0.5
hydrogel for the target object with length of 15 mm
(AVI)
DOI: 10.1021/acsami.7b01710
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ACS Applied Materials & Interfaces
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: liuz@scu.edu.cn (Z.L.).
*E-mail: chuly@scu.edu.cn (L.-Y.C.).
ORCID
Liang-Yin Chu: 0000-0002-2676-6325
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge support from the National
Natural Science Foundation of China (21490582, 81621062),
the Program for Changjiang Scholars and Innovative Research
Team in University (IRT15R48) and State Key Laboratory of
Polymer Materials Engineering (sklpme2014-1-01).
■
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15767 DOI: 10.1021/acsami.7b01710

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