Research Article

Cite This: ACS Appl. Mater. Interfaces 2019, 11, 3506−3515 www.acsami.org

Tough, Adhesive, Self-Healable, and Transparent Ionically

Conductive Zwitterionic Nanocomposite Hydrogels as Skin Strain
Sensors
Liufang Wang,†,‡ Guorong Gao,‡ Yang Zhou,‡ Ting Xu,‡ Jing Chen,‡ Rong Wang,‡ Rui Zhang,*,†
and Jun Fu*,‡
†
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai
200237, China
‡
Cixi Institute of Biomedical Engineering & Polymers and Composites Division, Ningbo Institute of Materials Technology &
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Engineering, Chinese Academy of Sciences, 1219 Zhongguan West Road, Ningbo 315201, China
*
S Supporting Information
Downloaded via LINKOPING UNIV on October 22, 2019 at 15:54:08 (UTC).

ABSTRACT: It is desired to create skin strain sensors

composed of multifunctional conductive hydrogels with
excellent toughness and adhesion properties to sustain cyclic
loadings during use and facilitate the electrical signal
transmission. Herein, we prepared transparent, compliant,
and adhesive zwitterionic nanocomposite hydrogels with
excellent mechanical properties. The incorporated zwitterionic
polymers can form interchain dipole−dipole associations to
offer additional physical cross-linking of the network. The
hydrogels show a high fracture elongation up to 2000%, a
fracture strength up to 0.27 MPa, and a fracture toughness up to 2.45 MJ/m3. Moreover, the reversible physical interaction
imparts the hydrogels with rapid self-healing ability without any stimuli. The hydrogels are adhesive to many surfaces including
polyelectrolyte hydrogels, skin, glasses, silicone rubbers, and nitrile rubbers. The presence of abundant zwitterionic groups
facilitates ionic conductivity in the hydrogels. The combination of these properties enables the hydrogels to act as strain sensors
with high sensitivity (gauge factor = 1.8). The strategy to design the tough, adhesive, self-healable, and conductive hydrogels as
skin strain sensors by the zwitterionic nanocomposite hydrogels is promising for practical applications.
KEYWORDS: tough hydrogels, adhesion, zwitterionic polymer, self-healing, strain sensors

1. INTRODUCTION proved adhesion is obtained at the expense of the mechanical

Polymer hydrogels with excellent performances, including
toughness,1−6 responsiveness,7−9 self-healing,10,11 and adhe-
siveness,12,13 have great potentials for applications in electronic
skin, biomedical sensors, soft robotics, and so on, and have
attracted great research interest. However, it is yet a challenge
to achieve ideal adhesion between hydrogels and most surfaces.
For example, conformal contacts of the sensors to the skin are
required to maximally convert the skin deformation into
electrical signals. However, many skin strain sensors are taped
to the skin, which may form gaps at the interface14 and is
uncomfortable. Enormous efforts have been made to prepare
integrative hydrogels with both conformal adhesion and
sensitive sensing. Sitti et al.15 prepared skin adhesive strain
sensors composed of microfibrillar films and silver nanoparticle
thin film-based strain sensors. The adhesion was enhanced by
cross-linking the viscous mushroom-shaped vinylsiloxane tips
directly on the skin surface. But the reusability was limited, that
is, the adhesion strength decreased by 48% after three cycles.
Zhang et al.16 prepared adhesive and conductive hydrogels by
combining the mussel-inspired polydopamine and conductive
functionalized single-wall carbon nanotubes. However, im-
properties because the free movement of molecular chains may
facilitate interactions between hydrogels and adherends but
reduce the stability of cross-linking in the hydrogels. Gao et
al.17 prepared adhesive hydrogels by introducing adenine and
thymine into the polyacrylamide backbone, which had
excellent adhesive properties for various solid materials but
low fracture strength (25 kPa). Liu et al.18 reported the
epidermal strain sensors with the addition of polydopamine
into poly(vinyl alcohol) hydrogels, whose modulus of
compression was 4.6 kPa. Practically, excellent mechanical
properties of adhesive hydrogels are required for skin strain
sensors, which can ensure high and stable performance during
applications. Meanwhile, the mechanical performance match-
ing the hydrogel and the skin can better avoid cohesive
fracture. Therefore, it is desired to prepare a hydrogel strain
sensor with reversible and compliant adhesion, toughness, and
high sensitivity.
Received: November 26, 2018
Accepted: December 28, 2018
Published: December 28, 2018

© 2018 American Chemical Society 3506 DOI: 10.1021/acsami.8b20755

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Scheme 1. Schematic Illustration to the Synthesis of Zwitterionic Nanocomposite Hydrogels
It is well-known that the positive and negative charges of the
overall neutral zwitterionic molecules make a high dipole
moment.19 Such strong dipolarity entitles excellent adhesion of
zwitterionic hydrogels to many surfaces through ion−dipole or
dipole−dipole interactions.20,21 In addition, the association of
zwitterionic polymers can provide physical cross-linking to
enhance the mechanical properties of hydrogels. The
zwitterions can assist the ion transportation along the highly
dipolarized skeleton to promote ion conduction, which endows
zwitterion hydrogels with good conductive properties.21
Hydrogels of zwitterionic betaine polymers are potential for
integrating multifunctionality on a single hydrogel such as
adhesiveness, conductivity, and so on. However, most of the
reported zwitterionic hydrogels22,23 are mechanically weak.
Haraguchi et al. 24 prepared nanocomposite hydrogels
comprised of zwitterionic polymers or copolymers. An effective
polymer−clay network was formed by ionic interactions
between the sulfobetaine polymers and clay platelets and
interchain associations of the zwitterionic group charges. The
hydrogels showed superior mechanical properties and well-
controlled thermosensitivities.
Here, we present a facile method to prepare zwitterionic
nanocomposite hydrogels physically crosslinked by exfoliated
Laponite XLG nanosheets with excellent mechanical proper-
ties, compliant adhesion, reliable self-healing, and high strain
sensitivity. The transparent hydrogels are comprised of
zwitterionic [2-(methacryloyloxy) ethyl]dimethyl-(3-sulfo-
propyl) ammonium hydroxide (SBMA) and 2-hydroxyethyl
methacrylate (HEMA) copolymers. They can be stretched to
2000% at a fracture strength up to 0.27 MPa and can adhere to
various substrates including hydrogels, skin, glasses, silicone
rubbers, and nitrile rubbers. The reversible interaction between
the zwitterionic nanocomposite hydrogels and the adherends
enables repeated adhesion and peeling. Moreover, the
hydrogels form a conformal interface between the zwitterionic
nanocomposite hydrogels and the skins with complex surface
topography and dynamic motions. The reversible physical
interactions make the hydrogels self-healable. Moreover, the
hydrogels have high conductivity and high sensitivity (GF =
1.8) with the increasing zwitterion content. These outstanding
properties make the zwitterionic nanocomposite hydrogels
promising for skin strain sensors to monitor the movement of
the body.
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2. EXPERIMENTAL SECTION
2.1. Materials. A synthetic hectorite “Laponite XLG” was
provided by Zhejiang Fenghong New Materials Co. Ltd. [2-
(Methacryloyloxy) ethyl]dimethyl-(3-sulfopropyl) ammonium hy-
droxide (SBMA, 97%), potassium persulfate (KPS, 99.5%), 2-
hydroxyethyl methacrylate (HEMA, 96%), 2-acrylamide-2-methyl-
propanesulfonic acid (AMPS, 98%), [2-(acryloyloxy)ethyl]trimethyl-
ammonium chloride solution (DAC, 80%), N,N′-methylenebis-
(acrylamide) (MBAA, 99%), and N,N,N′,N′-tetramethylethylenedi-
amine (TEMED, 99%) were purchased from Aladdin (Shanghai,
China). All these reagents were used without further purification.
Deionized water (18.2 MΩ at 25 °C) was prepared before use.
2.2. Preparation of Zwitterionic Nanocomposite Hydrogels.
Zwitterionic nanocomposite hydrogels were synthesized by free
radical polymerization with the presence of exfoliated clay platelets in
aqueous media. First, a uniform aqueous suspension of Laponite XLG
was prepared at ice-water temperature. Then HEMA, SBMA, and
initiator KPS were added to the clay suspension and stirred to
generate a homogeneous solution at ice-water temperature.
Subsequently, TEMED was added into the solution and stirred for
5 min. The solution was transferred into molds comprising a 1.5 mm
silicone rubber spacer between two glass plates. Free radical
polymerization was carried out at 25 °C for 24 h. A series of
synthesis formulations are shown in Table S1. The zwitterionic
nanocomposite hydrogels are denoted as LmSn hydrogels, with L for
Laponite XLG, S for SBMA, m for the concentration of clay (10−2
mol/L), and n for the mol % of SBMA in the total monomers. For
comparison, we also prepared the hydrogels with NaCl. During the
preparation process of the hydrogels, only the aqueous solution was
replaced by 1 mol/L NaCl solution.
2.3. Preparation of Polyelectrolyte Hydrogels. Polyelectrolyte
hydrogels were synthesized by using MBAA as the cross-linker for in
situ copolymerization of HEMA and AMPS (or DAC). As described
in previous studies,25 a solution of HEMA (2.3 g), MBAA (0.003 g),
KPS (0.0035 g), and AMPS or DAC in 3 mL deionized water was
prepared before TEMED was added into the mixture and stirred for 5
min. Finally, the solution was injected into molds made of two parallel
glass plates and a 1.5 mm silicone rubber spacer. Free radical
polymerization was conducted at 25 °C for 24 h. The synthesis
formulations are shown in Tables S2 and S3. We denote the Cx
hydrogels and Ay hydrogels as cationic and anionic hydrogels,
respectively. Herein, C refers to DAC and A refers to AMPS, whereas
x and y refer to the molar concentrations of ionic monomers (mol/L).
2.4. Tensile Tests. Mechanical performance was investigated by
using a Universal Testing Machine (Instron 5567) at room
temperature on dumbbell specimen (35 mm × 2 mm × 1.5 mm)
at 100 mm/min. The fracture toughness of the hydrogel was
calculated by integrating the area under the stress−strain curve.
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Figure 1. Photographs of (a) the as-prepared and (b) highly stretched L4S90 hydrogel. (c) The transparent L4S90 gels are used to adhere glass,
polyanionic (purple), and polycationic (yellow) hydrogels together. (d) The lap shear test of the C0.25−L4S90−C0.25 assembly. (e) The
compliant adhesion of L4S90 hydrogel to fingers. Scale bars, 10 mm. (f) The possible adhesion mechanisms including ion−dipole interaction and
dipole−dipole interaction between the LmSn hydrogels and the adherends.
Measurements on five specimens were conducted for each material
and the results were reported as mean ± standard deviation.
2.5. Lap Shear Tests. A Universal Testing Machine was used to
test the adhesion performance of the LmSn hydrogels by the lap shear
tests. A zwitterionic nanocomposite hydrogel (15 mm × 15 mm × 1.5
mm) was placed between two polyelectrolyte hydrogels, glass slides,
silicone rubbers, or nitrile rubbers (17 mm × 30 mm × 1.5 mm) to
form a sandwiched area of 15 mm × 15 mm. A contact pressure (100
g) was applied for 10 min to form a good contact before the tests. All
tests were performed at a shear rate of 50 mm/min at room
temperature. Measurements of each assembly were repeated at least
five times and the results were reported as mean ± standard deviation.
For the repeated adhesion, the zwitterionic nanocomposite
hydrogel sample was also used for the lap shear tests, where the
waiting time attached to the surface of substrates was 10 min. The
next test was conducted immediately after each test.
2.6. Measurement of Electrical Properties. The conductivity
of the LmSn hydrogels was measured by using a digital four-probe
tester (ST2258C, China). Besides, the electrochemical impedance
tests were also performed by using a Solartron 1470E multi-channel
potentiostat electrochemical workstation (Solartron Public Corp.,
Ltd). The impedance data were analyzed by using the ZView software
according to the Randles equivalent circuit. The resistance changes of
the zwitterionic nanocomposite hydrogels were obtained by using an
electrochemical analyzer/workstation (CHI600E, China). The gauge
factor is defined as GF = [(R − R0)/R0]/ε = (ΔR/R0)/ε, where R0
and R are the resistances of the original and stretched hydrogels,
respectively, and ε is the strain of the hydrogel.
3. RESULTS AND DISCUSSION
3.1. Toughness and Adhesiveness of Zwitterionic
Nanocomposite Hydrogels. The transparent zwitterionic
nanocomposite hydrogels were prepared by free radical
polymerization of SBMA and HEMA with the presence of
an exfoliated clay (Scheme 1). During the preparation process,
the introduction of the zwitterionic monomer SBMA into the
clay solution significantly decreased the viscosity and sup-
pressed the formation of a clay gel, which indicates the
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interaction between the clay platelets and the SBMA monomer
in aqueous solution. The zwitterionic nanocomposite hydro-
gels have excellent mechanical properties. As shown in Figure
1a,b, the L4S90 hydrogel can be stretched to 1000% strain
without fracture. After load release, the hydrogel can recover to
the original state in 4.5 min (Video S1). The repeated stretch
and release were performed. No significant changes in the gel
were observed by visual inspection, which implies that the
zwitterionic nanocomposite hydrogels show excellent tough-
ness and could be reused multiple times.
Moreover, the free zwitterionic groups of the LS hydrogels
can endow the hydrogels with unique adhesion to substrates
with charged groups or polar groups. Figure 1c shows that the
glass, polycation hydrogel, and polyanion hydrogel are
assembled together by using L4S90 hydrogels as the
intermediate layer. In contrast, the polycationic or polyanionic
hydrogel cannot directly adhere to the glass. The interfaces of
the assemblies are robust and could sustain stretching. As the
cationic C0.25 gel attached with a blue polyzwitterionic
nanocomposite hydrogel is stretched, the zwitterionic nano-
composite hydrogel (blue) is deformed along with the cationic
gel substrate without delamination until the fracture of the
cationic gel (Figure 1d).
More interestingly, the zwitterionic nanocomposite hydro-
gels are able to form stable and conformal adhesion to the
finger skin (Figure 1e). The L4S90 hydrogel well conforms
with the finger surface during the cyclic bending or stretching
of the finger, without delamination or forming gaps from the
finger surface (Video S2). Besides, the hydrogel can be easily
and completely peeled off from the skin without residues
(Figure S3). This result indicates an outstanding compliant
adhesiveness that is important for applications. This out-
standing adhesion of the hydrogels on the polyelectrolyte
hydrogels could be attributed to the dipole−dipole interactions
between the zwitterion moieties with the ionic groups (Figure
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Figure 2. Mechanical properties of LmSn hydrogels. (a) The tensile stress−strain curves and (b) fracture strain and fracture strength of L5S
hydrogels. (c) The tensile stress−strain curves and (d) fracture strain and fracture strength of LS90 hydrogels. The fracture toughness of (e) L5S
hydrogels and (f) LS90 hydrogels.
1f). Moreover, the −OH, −CN, −COOH, and −NH2
groups on many other substrates may also adhere with the
polyzwitterionic hydrogels through dipole−dipole interactions
with the −N+(CH3)3 and −SO3 groups (Figure 1f).
3.2. Tensile Properties. In contrast to many other
reported adhesive hydrogels with weak mechanical strength
and deformability,18,26 the zwitterionic nanocomposite hydro-
gels have outstanding mechanical properties. The zwitterionic
nanocomposite hydrogels exhibited high stretchability and
toughness, which may be related to the unique composition
comprised of the zwitterionic SBMA and the clay platelets.
Figure 2 shows the representative tensile stress−strain curves
of hydrogels. The changes in SBMA and Laponite XLG
contents obviously influence the stretchability, strength, and
toughness of the hydrogels.
Interestingly, both the fracture strain and strength increased
monotonously from 470 to 2000% and from 0.15 to 0.27 MPa,
respectively, as the SBMA content was increased from 50 to
90% (Figure 2a,b). Meanwhile, the fracture toughness of the
L5S hydrogels increased with the SBMA content, from 0.32 to
2.45 MJ/m3 (Figure 2e). As for the L4S and L6S hydrogels, a
similar dependence was observed (Figure S1). The fracture
strength of the LS90 hydrogels increased from 0.21 to 0.27 and
0.38 MPa as the clay concentration was increased to 4 × 10−2,
5 × 10−2, and 6 × 10−2 mol/L (Figure 2c,d). Correspondingly,
the fracture toughness of the LS90 hydrogels increased from
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1.60 to 2.44 and 2.88 MJ/m3 (Figure 2f). However, the
fracture strain increased first and then decreased slightly.
The excellent mechanical properties of the zwitterionic
nanocomposite hydrogels can be attributed to the ionic
interactions24 between the zwitterion and clay platelets and
the interchain associations27 of the zwitterionic groups to form
the physically cross-linked networks in the LmSn hydrogels
(Scheme 1). The increase of the SBMA and Laponite XLG
content facilitates the formation of denser networks, which can
dissipate more energy to toughen the hydrogels. Therefore,
one could tune the mechanical performance of the hydrogels
by varying the SBMA and clay content.
3.3. Adhesion Performance and Possible Mecha-
nisms. To quantitatively characterize the adhesion perform-
ance of the hydrogels, the lap shear tests have been conducted.
For this purpose, the zwitterionic nanocomposite hydrogel is
sandwiched between polyelectrolyte hydrogels, glasses, or
other materials (Figure 3a). The assemblies are stretched on
both ends until separation (adhesion failure) or fracture
(cohesion failure). Representative curves of adhesion shear
force vs displacement for each model are presented in Figures
3b,c and S4 (Supporting Information). The maximum force is
taken as the interface adhesion force when the interface
ruptures. In Figure 3d, the adhesion force of the L4Sn to the
C0.15 hydrogels was significantly increased with the increasing
SBMA content. In contrast, the adhesion force of the L4Sn
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Figure 3. (a) Schematic illustration of lap shear test. Representative curves of adhesion shear force vs displacement for (b) the L4S hydrogels to the
C0.15 hydrogels and (c) the L4S hydrogels to the A0.15 hydrogels. (d) The adhesion force of L4S hydrogels with different SBMA contents to
C0.15 hydrogels and A0.15 hydrogels. The adhesion force of L4S90 hydrogels to (e) polycation hydrogels and (f) polyanion hydrogels with
different ionic monomer contents.

Scheme 2. Schematic Illustration of the Surface of the Zwitterionic Nanocomposite Hydrogels

hydrogels to the A0.15 hydrogels first increased and
subsequently decreased with the increasing SBMA content.
At a high SBMA content from 70 to 90%, the adhesion force
was almost unchanged.
The charge density in the polyelectrolyte hydrogels has a
significant influence on the adhesion force. Figure 3e,f shows
the effect of DAC and AMPS contents on the adhesion force of
the L4S90 hydrogels to polyelectrolyte hydrogels. The
adhesion force of the L4S90 hydrogels to the polycationic
hydrogels increased with the DAC content. As the DAC
content was 0.25 mol/L, the adhesion of the L4S90 hydrogel
to the C0.25 hydrogel was so strong that the polyelectrolyte
hydrogel fractured instead of interface failure. Interestingly, the
adhesion force of the L4S90 hydrogels to the A hydrogels was
almost unaffected despite the change of the AMPS content.
The adhesive properties of zwitterionic nanocomposite
hydrogels are attributed to the charged groups of zwitterionic
polymers. The zwitterionic polymers with the cationic
quaternary ammonium groups and anionic sulfonate groups
3510
on the same monomeric unit exhibit neutral net charge, but
have high dipole moment. The charged groups can interact
with other charged groups or polar groups through ion−dipole
and dipole−dipole interactions28,29 (Figure 1f). Therefore, the
zwitterionic nanocomposite hydrogels can attach to other
materials through the interaction between the cationic groups
and anionic groups on LmSn hydrogel surfaces and charged
groups on other substrates.
Interestingly, the adhesion behaviors of zwitterionic nano-
composite gels to polyanionic gels are significantly distinct
from the polycationic hydrogels (Figure 3d−f). This could be
ascribed to the unique molecular structure of the SBMA
monomer. In the SBMA polymer, the anionic groups are
outreaching the dangling zwitterionic side groups. Therefore,
most anionic groups are pointing out the surface of the LmSn
hydrogels. This explains the observation that the adhesion
force between the zwitterionic nanocomposite hydrogels and
the polycationic hydrogels is larger than that for the
zwitterionic-polyanionic hydrogel pairs. The SBMA dipoles
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Figure 4. (a) Adhesion force of LS90 hydrogels with different XLG contents to C0.15 hydrogels. (b) The adhesion force of L4S90 hydrogels with
or without NaCl to C0.2 hydrogels. (c) The repeated adhesion between L4S90 hydrogels and C0.2 hydrogels. (d) The adhesion force of L4S90
hydrogels to various materials.
may adopt two different conformations on the gel surface,
depending on the crowdedness of the PSBMA chains. Scheme
2 illustrates the flat-on conformation at low PSBMA density
and the standing conformation of the zwitterion dipoles at the
overcrowded PSBMA surface. At the low SBMA content
regime, less zwitterionic side groups are available to interact
with cationic polymers. The cationic groups on the surface of
the LmSn hydrogels interact more easily with the anionic
groups on the A0.15 hydrogels surface. Increasing the SBMA
content contributes to the increase in the cationic groups on
the gel surface, which leads to an increase in the adhesion force
of the L4S hydrogels to the A0.15 hydrogels. In contrast, at the
high SBMA content regime, the zwitterionic groups may form
a saturated and tight conformation, which may make the
interface adhesion insensitive to the ionic monomer concen-
tration in the polyelectrolyte gels. The adhesion force of the
L4S hydrogels to the A0.15 hydrogels is roughly the same
when the SBMA content changes from 70 to 90%. In addition,
the adhesion force of the L4S90 hydrogels to polyanionic
hydrogels with different AMPS contents varies slightly. When
the SBMA content is 90%, the cationic groups on the surface
of the gel are limited and can equally interact with the anionic
groups in different polyanionic hydrogels. This explains the
observation that the change in the anionic monomer content
has little influence on the adhesion force.
The mechanical properties of the LS hydrogels can influence
the adhesion properties of the LS hydrogels to the
polyelectrolyte hydrogels. Figure 4a shows that the adhesion
force of the LmS90 hydrogels to the C0.15 hydrogels
significantly decreased with the increase in the clay content.
Meanwhile, the elastic modulus of the LmS90 hydrogels
dramatically increased with the clay content (Figure 2c). It has
been reported that the elastic modulus of the hydrogels has a
significant influence on the deformability, and thus the
adhesion behavior of the hydrogel surface.30 Here, with a
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high clay content, the polymer chains are adsorbed to the clay
nanosheets, leading to a high crosslink density and high
modulus. Since the zwitterionic contents in these gels are
almost the same, the interface adhesion is mainly affected by
the compliance, or the reciprocal of the modulus of the gels.
This explains the decrease of the adhesion force with the
increasing clay content.
To further illustrate the adhesion properties of the
zwitterionic nanocomposite hydrogels through ion−dipole or
dipole−dipole interactions, NaCl was introduced into the
LmSn hydrogels, only to obtain the same mechanical
properties as the hydrogels without NaCl (Figure S1). In the
presence of NaCl, the adhesion force of the L4S90 hydrogel to
the C0.2 hydrogels significantly decreases by 43% in
comparison with that of the L4S90 to C0.2 hydrogel pair
free of salt (Figure 4b). The Na+ and Cl− ions could interact
with the charged groups of the zwitterions, and thus shield the
interaction between the SBMA moieties and the charged
groups in the polyelectrolyte hydrogels.
The zwitterionic nanocomposite hydrogels can repeatedly
adhere to the adherends through reversible physical
interactions. Repeated lap shear tests were carried out
immediately after each test and the results are shown in
Figure 4c. After five cycles, the adhesion force of the L4S90
hydrogel to the C0.2 hydrogels slightly decreased. It may be
attributed to the contamination or slight damage of the sample
surface after each cycle, which may reduce the extent of
interactions. The adhesion force after multiple cycles was
almost unchanged, which allows the gel to be reused multiple
times. Moreover, the zwitterionic nanocomposite hydrogels
can also adhere to silica rubber, glasses, and nitrile rubber, as
shown in Figure 4d. The polar groups (−OH of glasses, −C
N of nitrile rubber) in these materials may offer interactions
with the zwitterionic nanocomposite hydrogels.
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Figure 5. (a) Conductivity of L4S hydrogels with different SBMA contents. (b) The resistance change of L4S90 hydrogel before facture and after
self-healing. (c) The self-healing process. (d) Representative tensile stress−strain curves of the as-prepared and self-healed L4S90 hydrogels with
different healing times.
Figure 6. (a) Resistance ratio−strain curve of the L4S90 hydrogel. (b) The resistance ratio of the L4S90 hydrogel strain sensor with reversible
bending and unbending of a finger.
3.4. Conductivity and Strain Sensitivity. The zwitter-
ionic nanocomposite hydrogels have good conductivity and
high strain sensitivity. The conductivity originates from the
free ions from clay in the hydrogel network, and thus is
featured as ionic conductivity. In contrast to the well-known
electronic conductive hydrogels, the ion conductive hydrogels
may behave differently under direct current (DC) and
alternating current (AC). Therefore, the conductivity or
resistance of the zwitterionic nanocomposite hydrogels is
measured by using a four-point probe method and the
electrochemical impedance spectroscopy (EIS). By using the
four-point probe tester with DC, the conductivity of the L4S
hydrogels significantly increases from 0.0066 to 0.24 S/m as
the SBMA content increases from 50 to 90 mol % (Figure 5a).
On the other hand, the conductivity of the L4S hydrogels by
EIS under AC shows an increase from 0.076 to 0.099 S/m with
the increasing SBMA content (Figure S5). The conductivity
changes obtained by the two test methods are consistent. The
zwitterionic nature makes the cationic and anionic counterions
of polyzwitterions to easily separate during ion migration,
ensuring a high ionic conductivity.31,32 A previous study33 also
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discovered that the ion movement could be enhanced by the
weak interactions between the mobile ions and the zwitterionic
polymers. The zwitterionic moieties can assist the ion
conduction, and thus the hydrogels behave conductive with
mobile ions.34
On the other hand, the zwitterionic nanocomposite
hydrogels have the self-healing capability due to the reversible
physical cross-linking in the hydrogels. Figure 5b compares the
resistance of the L4S90 hydrogel before facture and after self-
healing. When the L4S90 hydrogel was cut with a razor blade,
the resistance increased immediately and sharply. Subse-
quently, the resistance recovered to the original level by
contacting the two fractured parts together in 11 s (Figure 5c).
On the other hand, the mechanical self-healing is also
systematically investigated. Tensile test results of the as-
prepared and self-healed hydrogels are shown in Figure 5d.
After 1 h healing, the hydrogels can be stretched to 350%.
After 24 h, the healed hydrogels can be stretched to 0.17 MPa,
and 1700%, with a healing efficiency of about 74% in terms of
the fracture strength. Therefore, the zwitterionic nano-
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composite hydrogels have self-healing properties in both
mechanical properties and conductivity.
The zwitterionic nanocomposite hydrogels can serve as
wearable soft strain sensors to monitor human activities. As
shown in Figure 6a, the resistance of the hydrogel increased
with increasing strain. When the L4S90 hydrogel was stretched
to 100%, the resistance increased to around 280%, which
exhibited high strain sensitivity (GF = 1.8). The L4S90
hydrogels can adhere on the index finger without tapes because
of the compliant adhesion of the hydrogels to skins. When
bending the index finger, the relative resistance of the hydrogel
sensor increases. After straightening the index finger, the
relative resistance rapidly returns to the initial value (Figure
6b). The relationship between the relative resistance of the
stretched hydrogel and the strain is consistent with the result
in Figure 6a. Moreover, the determined strain of bending finger
(about 40%) is similar to that in other reported sensors (35−
45%).35,36 It is promising to utilize the zwitterionic nano-
composite hydrogels to precisely monitor the real-time change
of human motion.
3.5. Discussions. Despite increasing progress in con-
ductive hydrogels in the literature, it remains an open issue to
combine adhesion and conduction in hydrogels. For practical
applications, conductive hydrogels attaching firmly to other
surfaces are in favor of the electrical signal transmission. We
synthesized transparent, compliant, and adhesive zwitterionic
nanocomposite hydrogels that can conformally adhere to the
skin without the tape. Hydrogels with robust adhesion may
sacrifice mechanical properties and are susceptible to damage
at large strains. There are few examples of conformally
adhesive hydrogels that can also possess excellent mechanical
properties. The poly(vinyl alcohol) hydrogel containing
polydopamine for the epidermal strain sensor18 can be easily
reformed to various shapes and the modulus of compression is
4.6 kPa. The bioinspired mineral hydrogels are composed of
amorphous calcium carbonate nanoparticles physically cross-
linked by polyacrylic acid and alginate chains for the ionic
skin.37 The maximum fracture stress of the hydrogel is 6 kPa,
although the ionic skin is compliant with curved or dynamic
surfaces. We prepared the zwitterionic nanocomposite hydro-
gels that show a large strain up to 2000% and the fracture
strength up to 0.27 MPa. Moreover, the hydrogels can rapidly
recover to its original state after the release of force. These
properties allow the hydrogels to achieve high and stable
performance and match with the modulus of skin (0−600
kPa).38 More interestingly, the transparent, tough, and
adhesive zwitterionic nanocomposite hydrogels can also
conduct through the mobile ions and possess good
conductivity (up to 0.099 S/m), which is comparable with
that of some electronically conductive hydrogels.39 In addition,
the zwitterionic nanocomposite hydrogels have high sensitivity
and is superior to previously reported ionically conductive
hydrogels. Wan et al.14 reported multifunctional hydrogels with
synergistic soft and hard hybrid networks, showing a gauge
factor of 0.478. Yang et al.40 designed mussel-inspired cellulose
nanocomposite tough hydrogels with a gauge factor of 1 (0% <
strain < 80%). In short, the zwitterionic nanocomposite
hydrogels are advantageous beyond most ionic conductive
hydrogels in the literature.
The outstanding mechanical properties, reversible and
compliant adhesion, self-healing capability, and good con-
ductivity and sensitivity are primarily attributed to the
introduction of zwitterions into the nanocomposite hydrogels.
3513
Research Article
The zwitterion polymer can interact with the clay platelets by
ionic interaction and form self-association, which can provide
more physical cross-linking to dissipate energy. Moreover, the
free zwitterionic groups can interact with other charged or
polar groups by the ion−dipole interaction or dipole−dipole
interaction so that the zwitterionic nanocomposite hydrogels
can attach to certain surfaces including polyelectrolyte
hydrogels, glasses, nitrile rubber, and skins. The physical
interactions in hydrogels can endow the hydrogels with self-
healing properties and reversible adhesive properties. More-
over, the zwitterionic groups can act as carriers to promote ion
conduction and the hydrogels have high sensitivity in strain
conduction.
With comprehensive properties, the transparent zwitterionic
nanocomposite hydrogels can serve as skin strain sensors to
monitor the movement of the body. The excellent mechanical
properties and self-healing capability can extend the life of the
sensors. Moreover, the reversible and compliant adhesion can
enhance the intimate contact between the sensors and skins to
amplify the transmission of signals. Furthermore, the
zwitterionic nanocomposite hydrogels can be used as solid
electrolytes because the hydrogels are mechanically stable and
safe, and can simultaneously play multiple roles of an
electrolyte, a separator, and a binder.
Despite the abovementioned merits, it is a challenge to
achieve fast and effective self-healing of hydrogels, which is
critical for the lifespan of electronic devices and to improve
stability. The zwitterionic nanocomposite hydrogels possess
self-healing properties due to the existence of physical
interactions in hydrogels. However, the fast self-healing is
limited and further efforts should be devoted to achieve fast
and effective self-healing of hydrogels for practical applications.
4. CONCLUSIONS
In summary, we have demonstrated a facile strategy to prepare
tough and adhesive hydrogels by introducing the zwitterionic
monomer into the nanocomposite hydrogels. The transparent
zwitterionic nanocomposite hydrogels simultaneously possess
satisfying mechanical properties, compliant adhesion, reliable
self-healing capability, and high sensitivity in conductivity,
which can make the LmSn hydrogels ideal candidates for
wearable skin strain sensors. In addition, the zwitterionic
nanocomposite hydrogels with excellent mechanical properties
and the compliant adhesion can be applied to more aspects,
such as wound dressing. In brief, the strategy to synthesize the
zwitterionic nanocomposite hydrogels by the free radical
polymerization of SBMA and HEMA in the exfoliated clay has
shed new light on preparing tough and adhesive hydrogels.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.8b20755.
Formulations of zwitterionic nanocomposite hydrogels,
polycation hydrogels, and polyanion hydrogels; typical
tensile stress−strain curves of L4S hydrogels, L5S
hydrogels, and L4S90 hydrogels with or without 1
mol/L NaCl; typical tensile stress−strain curves and
fracture strength of polycation hydrogels and polyanion
hydrogels; stripping process of the L4S90 hydrogel from
the skin; adhesion shear force vs displacement curves of
the zwitterionic nanocomposite hydrogels to polyelec-
DOI: 10.1021/acsami.8b20755
ACS Appl. Mater. Interfaces 2019, 11, 3506−3515
ACS Applied Materials & Interfaces
trolyte hydrogels; electrochemical impedance spectros-
copy (EIS); and conductivity of the L4S hydrogels with
different SBMA contents (PDF)
Repeated stretching and releasing of the L4S90 hydrogel
(AVI)
Compliant adhesion between L4S90 hydrogel and skins
and the easy stripping process (AVI)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: r.zhang@ecust.edu.cn (R.Z.).
*E-mail: fujun@nimte.ac.cn (J.F.).
ORCID
Rong Wang: 0000-0003-1971-0865
Jun Fu: 0000-0002-8723-1439
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21574145, 51873224, 21374029), the
Natural Science Foundation of Zhejiang Province
(LQ16E030002, LY17E030011), and the Natural Science
Foundation of Ningbo (2017A610057, 2016A610255). We are
indebted to Professor Xiayin Yao and Gaozhan Liu for
assistance in the electrochemical impedance spectroscopy
(EIS) measurements.
■
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3515 DOI: 10.1021/acsami.8b20755

ACS Appl. Mater. Interfaces 2019, 11, 3506−3515