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org Research Article

Polyacrylamide/Chitosan-Based Conductive Double Network

Hydrogels with Outstanding Electrical and Mechanical Performance
at Low Temperatures
Jing Cong, Zhiwei Fan, Shaoshan Pan, Jie Tian, Weizhen Lian, Shan Li, Sijie Wang, Dongchang Zheng,
Chunguang Miao, Weiping Ding, Taolin Sun, and Tianzhi Luo*
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ABSTRACT: Hydrogel-based electronics have received growing attention because of their great flexibility and stretchability.
However, the fabrication of conductive hydrogels with high stretchability, excellent toughness, outstanding sensitivity, and low-
temperature stability still remains a great challenge. In this study, a type of conductive hydrogels consisting of a double network
(DN) structure is synthesized. The dynamically cross-linked chitosan (CS) and the flexible polyacrylamide network doped with
polyaniline constitute the DN through the hydrogen bonds between the hydroxyl, amide, and aniline groups. This type of hydrogels
displays excellent mechanical performance, striking conductivity, and remarkable freezing tolerance. The flexible electronic sensors
based on the double-network hydrogels demonstrate superior strain sensitivity and linear response on various deformations.
Additionally, the good antifreezing property of the hydrogels allows the sensors to exhibit excellent performance at −20 °C.
KEYWORDS: hydrogel, double network, toughness, conductivity, polyaniline, chitosan, polyacrylamide

1. INTRODUCTION made to synthesize tough conductive hydrogels with tunable

Hydrogels are composite materials composed of a large amount
of water and three-dimensional (3D) polymer networks.
Conductive hydrogels are a special type of hydrogels that can
transform external stimuli into a variation of electrical signals by
adding conductive materials (e.g., graphite materials1 and
carbon nanotubes2), free ions,3,4 conducting polymers (e.g.,
polyaniline (PANI),5,6 polypyrrole (PPy),7,8 poly(3,4-ethyl-
enedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS),9,10
and polythiophene (PTh)11) or liquid metals12 to the polymer
network to achieve conductivity. Because of the intrinsic
softness, deformability, biocompatibility, and unique electrical
properties, the conductive hydrogels become the promising
flexible sensors in the fields of biomimetic skin, human-machine
interfaces, implantable medical devices, wearable electronics,
and soft robots.13
Tough conductive hydrogels with superior mechanical and
electrical properties are more intriguing materials for practical
applications. In the past few years, several attempts have been
properties.14−17 However, these conductive hydrogels exhibited
weak elasticity, limited stretchability, and low toughness,
restraining their application as flexible wearable devices. During
a large stretch, the hydrogels undergo plastic deformation and
structure destruction, inducing incompetent shape recovery and
striking strength reduction.13 Thus, it is desirable to design novel
conductive hydrogels with high extensibility and stable
conductivity under large deformations. Recently, a new type of
hydrogels with a double network (DN) was developed by
introducing a dynamic cross-linking network into a polymer
Received: May 11, 2021
Accepted: July 6, 2021
Published: July 16, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsami.1c08421

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network. Such a DN structure enables the hydrogels to achieve
recoverable and reconfigurable structures after a large
deformation, resulting in remarkable stretchability, high tough-
ness, and rapid recovery in shape and mechanics.13
High sensitivity and linearity are pivotal for the feasibility and
reliability of hydrogel sensors,18 which relies on the stable
conductive network and free ions.19 At present, most conductive
hydrogels usually show a nonlinear dependence of sensitivity on
strain, presumably due to the damage of the conductive network
during deformation.20 Hence, it remains a challenge to fabricate
conductive hydrogels with good linearity and high sensitivity.
To date, the application of multifunctional hydrogels has been
intensively explored in the fields of tissue engineering,21−24 drug
release,25−27 and soft electronics.4,28,29 Most research was
focused on improving the mechanical properties and function-
alities of materials, whereas little attention has been paid to
overcome the drawbacks of the hydrogels under extreme
conditions, including low temperature, hypoxia, high-dose
exposure of ultraviolet (UV).30 For example, traditional
conductive hydrogels tend to freeze below 0 °C and lose their
elasticity and electrical conductivity, which limits their usage at
low temperatures.31,32 However, there is a pressing demand for
applying hydrogels in certain extreme environments.33,34
Here, we report a type of novel multifunctional conductive
hydrogels with high stretchability, excellent toughness, out-
standing sensitivity, remarkable frost resistance, and UV
radiation shielding. The hydrogels have a DN composed of
dynamically cross-linked chitosan (CS) and a flexible poly-
acrylamide (PAAm) network with PANI doping (Figure 1).
Figure 1. Construction of conductive dual-network hydrogel sensors.
(a) Schematic illustration of the synthesis of the interpenetrating
PANI/CS-PAAm ionic−covalent DN hydrogels. SEM images of the
ACPC hydrogel (b1), the PCPC hydrogel (b2) and the PCPD hydrogel
(b3).
These two networks interact through the hydrogen bonds
between the hydroxyl, amide, and aniline groups, as well as a
high concentration of salt ions, providing the hydrogels with
excellent mechanical performance, striking conductivity, and
good freezing tolerance.35−37 Additionally, the flexible elec-
tronic sensors assembled from the DN hydrogels exhibit
superior sensitivity on detecting stretching and bending, as
well as human activity, including microexpressions, joint
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motions, and daily exercises. At last, the ultrastrong UV
resistance and great freezing tolerance allow for the applications
of the hydrogels in extreme environments.
2. EXPERIMENTAL SECTION
2.1. Materials. All reagents in this research were used as received
without purification. Acrylamide (AAm, 99%), aniline (ANI, 99.5%),
and 2, 2′-azobis(2-methyl-propionamidine) dihydrochloride (V-50,
97%) were purchased from Aladdin Reagent Co., Ltd., China. N, N′-
methylenebis(acrylamide) (MBAA, 99%) was purchased from Sigma-
Aldrich. Ammonium persulfate (APS, 98%) and hydrochloric acid
(37.5 wt %) were purchased from Sinopharm Chemical Reagent Co.,
Ltd., China. Short-chain CS (degree of deacetylation >90%, viscosity 45
mPa s for 1% (w/v) solution) was purchased from Jinhu Company,
China. Ammonium sulfate ((NH4)2SO4) was purchased from Shanghai
Macklin Biochemical Co., Ltd., China.
2.2. Synthesis of Conductive Hydrogels. The PANI/CS-PAAm
ionic−covalent DN hydrogels were fabricated via three steps. Briefly,
0.5 g of CS was added to 10 mL of 0.5 M HCl to form transparent
solvents under stirring in a 60 °C water bath. After the solvents returned
to room temperature (RT), 2.13 g of AAm, 16.2 mg of MBAA, and 8.14
mg of V-50 with a certain amount of ANI were added and stirred well.
After being degassed by ultrasonic cleaning for 5 min, the solution was
injected into a mold that comprised two glass plates separated using a
silicone rubber spacer. Free radical polymerization of AAm monomer,
with MBAA as the cross-linker and V-50 as the thermal initiator, was
carried out at 50 °C for 12 h in a thermotank to generate the PAAm
composite hydrogel. Subsequently, the PAAm composite hydrogel was
immersed in 200 mL of 1 M APS solution to initiate oxidation
polymerization of ANI for 24 h at 4 °C. Finally, the PANI/PAAm
composite hydrogel was immersed in different concentrations of
(NH4)2SO4 solutions to form the PANI/CS-PAAm ionic−covalent
DN hydrogels.
2.3. Fourier-Transform Infrared Spectroscopy Measure-
ments. The Fourier-transform infrared (FT-IR) spectra of CS, CS-
PAAm, and PANI/CS-PAAm (PCPD) were recorded in the solid state
using KBr pellets. A Nicolet 8700 IR spectrophotometer was used to
record the spectra in the range of 4000−400 cm−1.
2.4. Mechanical Tests. The hydrogel samples were tested using a
SUST CMT5000 testing machine (SUST Inc., Zhuhai), with a 500 N
load cell at RT. Three samples were prepared for each hydrogel. For the
tensile tests, the hydrogels were cut into dumbbell-shaped samples with
2 mm inner width, 10 mm gauge length, and 1−2 mm thickness
according to the GB/T-528-2009 standard. The pulling speed was set
to 50 mm/min for tensile tests. For the cyclic tensile test, the hydrogels
were cut into dumbbell-shaped samples with an inner width of 4 mm
and a gauge length of 30 mm, and the loading−unloading speed was set
to 100 mm/min.
The tensile stress σ was determined by the ratio between load force F
and the cross-sectional area A0, that is, σ = F/A0. The tensile strain ε was
calculated using the formula: ε = (l − l0)/l0, (l is the final length, and l0 is
the original length of the sample). The elastic modulus (E) was
calculated from the slope at strain in the range 5−15% of the stress−
strain curve. The toughness is calculated by the area enclosed by the
stress−strain curve and the strain axis. The dissipated energy (U) was
obtained by calculating the area of the loading−unloading curve.
2.5. Mechanics of Hydrogel at Subzero Temperature. The
mechanical properties of hydrogels at subzero temperatures were
measured using an Instron 5965 Instrument (Instron Inc., MA USA)
together with an environmental chamber (FUYIDA WGDY-6300S)
that adopts a single-stage compressor unit to control the ambient
temperature and humidity. Before the test, each specimen was
maintained at the testing temperature for 20 min to ensure that the
temperature of the specimen was the same as that of the environment.
The elongation rate at subzero temperatures was 50 mm/min.
2.6. Microstructural Characterization. Scanning electron
microscopy (SEM) was conducted on a GeminiSEM 500 (ZEISS,
Germany). The hydrogels were quenched in liquid nitrogen, fractured,
and freeze-dried. The fracture surfaces of the specimens were sputtered
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Figure 2. Mechanical properties of the PANI/CS-PAAm DN hydrogels. (a) Stress−strain curve of the ACPC hydrogel, PCPC hydrogel, and PCPD
hydrogel. (b) Corresponding elastic modulus and toughness of the hydrogels in (a). (c) Representative tensile behaviors of the PANI/CS-PAAm
hydrogels with different ANI content. (d) Elastic modulus and toughness of the hydrogels in (c). (e) Representative tensile behaviors of the PANI/CS-
PAAm hydrogels with different CS contents. (f) The elastic modulus and toughness of the hydrogels in (e). The SEM images of freeze-fractured
surface of the 2.5 v/v% (g1), 5 v/v% (g2), and 7.5 v/v% (g3) ANI hydrogels. The SEM images of the freeze-fractured surface of the 3% (h1), 5% (h2),
and 7% (h3) CS hydrogels.

with a thin layer of gold and examined by SEM. The microstructures ΔR R − R0

=
were observed using a secondary electron imaging detector at an R0 R0 (1)
accelerating voltage of 3 kV.
2.7. Conductivity Measurement. The conductivity of as- where R0 and R are the initial and real-time resistance, respectively. The
prepared hydrogels was measured using an inductance, capacitance, conductivity σ was calculated using the following equation:
and resistance (LCR) meter (TH2832) at an alternating current (AC) L
voltage of 1 V and a sweeping frequency ranging from 0.1 to 100 kHz. σ=
RS (2)
2.8. Determination of Water Content. The hydrogels were
weighed on a balance before drying. Afterward, the hydrogels were where L is the distance between adjacent electrodes, R is the resistance
dried in an oven at 50 °C until the weight remained constant. The of the hydrogels, and S is the cross-sectional area of the hydrogels. The
weight loss of hydrogels was attributed to the mass of water. The water gauge factor (GF) is defined as follows:
content (wt %) was defined as the mass percentage of water in the
ΔR R − R0
hydrogels relative to the total weight of the hydrogels. GF = =
2.9. Differential Scanning Calorimetry Analysis. Differential R 0ε R 0ε (3)
scanning calorimetry (DSC) measurement was performed using TA where ε is the strain.
38
Q2000 at a rate of 1 °C min−1 between −80 and 25 °C under nitrogen 2.11. Frostbite Tests on the Back Skin of Rats. Five male Wistar
protection. IGS rats (purchased from Charles River Laboratories International,
2.10. Strain-Sensing Tests. An LCR meter (TH2832) was Inc.) with a weight of 300−310 g were used for the frostbite test. The
combined with a universal tensile tester (SUST CMT5000) to measure back skin of each rat was divided into three sections: (a) unprotected
the strain responsiveness of the DN hydrogels. The hydrogel samples area, (b) PANI/CS-PAAm composite hydrogel-protected area, and (c)
were fixed on the tensile fixture. Several metal wires connected the PANI/CS-PAAm DN hydrogel-protected area. The thicknesses of the
samples to the material electrical performance test system to record the hydrogels on b area and c area were 1.46 and 2.23 mm, respectively. The
real-time resistance. The stretching frequency was fixed at 1/24 Hz rats were anesthetized by the intraperitoneal injection of pentobarbital
(small deformation) and 1/48 Hz (large deformation). The relative (1 wt %, 5 mL kg−1). Subsequently, the hair on the rat back was softened
resistance change was calculated using the following formulas: with depilatory cream and shaved off to expose the underneath skin.

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Figure 3. Cyclic energy dissipation of the DN hydrogel. (a) Comparison of the hysteresis loops for different ANI contents (fixed 5% CS) at a strain of
600%. (b) Calculated dissipated energy and the dissipation coefficient of the hydrogels in (a). (c) Comparison of the hysteresis loops for different CS
contents (fixed 7.5 v/v% ANI) at a strain of 600%. (d) Calculated dissipated energy and dissipation coefficient of the hydrogels in (c). (e) Cyclic
loading−unloading curves under different strains (200, 300, 400, 500, and 600%). (f) Corresponding dissipated energy and energy dissipation rate in
every cycle. (g) Stress change of 1000 cycles of continuous cyclic stretching (strain is fixed at 50%). Insets are the stress curves of 1−50, 500−550, and
950−1000 cycles, respectively. The mechanical behaviors of the DN hydrogels subjected to different loadings: (h1) stretching, (h2) twisted stretching,
(h3) knotted stretching, and (h4) cross-over stretching.

Stainless-steel coins frozen using liquid nitrogen served as the cooling
source and were attached to the exposed rat skin for 30 s. After the
frostbite test, the rats were euthanized by excess ether, and the marked
skin was cut and fixed in 10% formalin buffer for subsequent histological
observation. The fixed tissues were dehydrated, verified, and finally
embedded in paraffin. After hematoxylin−eosin (H&E) staining,
histological observations were performed on a digital pathology
scanner (Pannoramic DESK, P-MIDI, P250, 3D HISTECH, Hungary).
The animal experiments were conducted in accordance with the
protocols approved by the local ethical committee and the
administration office of laboratory animal of China.
2.12. Ultraviolet−Visible Absorbance. Ultraviolet−visible
(UV−vis) absorption spectra were measured using a scanning UV−
vis spectrometer (BioTek). The thin sheets of the hydrogels were
prepared by spin-coating. The gel thickness was about 50 μm. The
optical attenuation of the hydrogels was measured in the range of 200−
900 nm using the UV−vis spectrometer. The absorption coefficient of
the hydrogels was obtained by normalizing the absorbance to the gel
thickness.
2.13. Rheological Measurement. The dynamic rheological
measurements of the hydrogels were carried out on a rheometer
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(Physica MCR 301) with a rotor-plate geometry (25 mm in diameter)
under steady shear. All the experiments were conducted at a RT of 25
°C.
3. RESULTS AND DISCUSSION
3.1. Fabrication of the PANI/CS-PAAm DN Hydrogels.
The hydrogel synthesis is illustrated in Figure 1a. First, the
PAAm hydrogel was synthesized by free radical copolymeriza-
tion of AAm monomers at 50 °C for 12 h with MBAA as the
cross-linker and V-50 as the thermal initiator, in addition to the
ANI monomers and short-chain CS. Subsequent in situ
oxidation of the ANI by APS generated PANI doping in the
hydrogel, converting the transparent hydrogel to dark green.
Compared with CS, the CS-PAAm composite hydrogel and
PANI/CS-PAAm composite hydrogel displayed a red shift of
the characteristic peak (3450 cm−1) of −OH in the FT-IR
spectra (Figure S1),which indicates that there are hydrogen
bonds between the aniline groups, the hydroxyl groups, and the
amide groups.3,39−41 It was reported that the hydrogen bonds
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Figure 4. Mechanical characterizations of the hydrogels with different volume fractions of (NH4)2SO4 at different temperatures. The stress−stretch
curves were measured at different temperatures for the hydrogels soaked in different (NH4)2SO4 solutions: (a) 0 wt % (NH4)2SO4, (b) 15 wt %
(NH4)2SO4, (c) 30 wt % (NH4)2SO4, and (d) 43.47% (NH4)2SO4. (e) Hydrogel displayed high stretchability in the environmental chamber at −20
°C. (f) Biphasic behavior of the ultimate tensile strain of the hydrogels in (a−d) (lines are for eye guidance only). (g1) Flexible and deformable DN
hydrogel after being stored at −20 °C for 12 h. The hydrogel would be bent 180° (g2), twist-stretched (g3), and stretched (g4) at −20 °C.

Figure 5. Frostbite experiments on the rat’s back skin to demonstrate the cold tolerance of the PANI/CS-PAAm hydrogel. (a) Schematic diagram of
the frostbite model. (b) Composite hydrogel and DN hydrogel were transformed from the normal temperature state to the frozen state (ii is a
composite hydrogel, iii is a DN hydrogel). (c) Extremely cold coins attached on the (i) bare skin, (ii) composite hydrogel-protected skin, and (iii)
PANI/CS-PAAm DN hydrogel-protected skin. The skin before (c1) and after the frostbite (c2). Histological microscopy images of the bare skin (di)
and skin protected by the composite hydrogel (dii) and the DN hydrogel (diii).

could facilitate the stabilization of the CS chains within the in a highly concentrated ammonium sulfate (43.47%
composite hydrogel. Finally, immersing the composite hydrogel (NH4)2SO4) solution allowed the homogeneous CS chains to
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Figure 6. Conductivity and sensitive response of the DN hydrogel sensors. The conductivity of the PANI/CS-PAAM DN hydrogels with (a) different
various contents of ANI and (b) various contents of CS. (c) Conductivity of hydrogels immersed in 0 wt %, 15 wt %, 30 wt %, and 43.47% (NH4)2SO4
solutions at 25, 0, −10, −20, and −30 °C. (d) Real-time relative resistance variation during the stretching process. (e) and (f) Time-dependent relative
resistance changes of the hydrogel sensor upon monitoring multiple-scale strain. Brightness variation of the LED bulb in an electrical circuit containing
the DN hydrogel at a strain of 0% (g1), 100% (g2), and 200% (g3).

Figure 7. Sensing performance of wearable sensors assembled from the DN hydrogels at RT and low temperature. The sensing of the finger bending
(a) at RT (b) and −20 °C (c), respectively. (d) Comparison of the resistance change of a finger at RT and −20 °C at different bending angles. The
sensing of various subtle actions: wrist bending (e), swallowing (f), and microexpression (g).

undergo phase separation and create an ionically cross-linked
network via the electrostatic interaction between N-glucosamine
and anion.42 The rigid PANI doping and newly formed CS
network evenly interpenetrated with the tough PAAm network,
forming a DN and introducing a synergetic effect on the strength
and toughness of the composite hydrogels. The formed CS
network served as a reversible “sacrificial bond” to consume
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energy, contributing to the repeatable energy dissipation and
outstanding mechanical performance of the DN hydrogels. The
treatment with the concentrated (NH4)2SO4 solution exhibited
four major effects: (1) creating dynamic cross-links of CS to
enhance the mechanical performance of the hydrogel; (2)
endowing the hydrogel with ionic conductivity; (3) rendering
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Figure 8. Summarized data of the properties of the DN hydrogels. (a)
Radar chart of the properties of the hydrogels with different contents of
ANI. (b) The radar chart of the properties of the hydrogels with
different contents of CS. (c) Radar chart of the properties of the
hydrogels treated with different (NH4)2SO4 solutions. (d) Comparison
of the GF at different strains between this work and published hydrogel
strain sensors at RT. All the properties in (a−e) are normalized to their
maxima such that all the data falls in the range of [0,1.0].
the hydrogel freezing tolerance; (4) making the CS chain more
entangled with the polyacrylamide main network.
The microstructures of the hydrogels were characterized by
SEM. The freeze-fractured surfaces of the ANI/CS-PAAm
composite (ACPC) hydrogel (Figure 1b1), PANI/CS-PAAm
composite (PCPC) hydrogel (Figure 1b2), and PANI/CS-
PAAm DN (PCPD) hydrogel (Figure 1b3) exhibited distinct
morphologies. The PAAm network containing short chains of
CS was a relatively loose structure with a large pore size (Figure
1b1) that is prone to mechanical damage during stretching. The
PANI forms continuous doping within the CS-PAAm matrix
(Figure 1b2), creating a denser network with a smaller pore size.
The interpenetrating structures were potentially beneficial for
the mechanical properties and conductivity of the gels. The
addition of the (NH4)2SO4 solution introduced a more densely
cross-linked CS network, further reducing the pore size (Figure
1b3).
3.2. Outstanding Mechanical Performance. The pres-
ence of PANI and CS is crucial for the mechanical properties of
the resultant hydrogels. Tensile tests (Figure 2a) quantitatively
revealed the striking enhancement of the mechanical strength:
the PANI/CS-PAAm DN hydrogel reached a high tensile stress
of 2.62 MPa compared to 55.1 and 93.93 kPa for the ACPC
hydrogel and PCPC hydrogel, respectively. Additionally, the
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elastic modulus of the PCPD hydrogel was 253.79 ± 22.79 kPa,
which is almost fivefold higher than that (40.02 ± 1.25 kPa) of
the ACPC hydrogel (Figure 2b). Moreover, the toughness of
PCPD hydrogel achieved a value of 8.67 ± 0.93 MJ m−3,
approximately 140 times higher than that (0.062 ± 0.0018 MJ
m−3) of the ACPC hydrogel.
To study the effect of ANI, we compared the tensile behaviors
of the hydrogels with 5% CS and different contents of ANI
(Figure 2c). The ultimate tensile strength (UTS) increased from
1.83 MPa (2.5 v/v% ANI) to 2.05 MPa (5 v/v% ANI) and 2.62
MPa (7.5 v/v% ANI), while the ultimate tensile strain (εu)
increased from 833% (2.5 v/v% ANI) to 898% (5 v/v% ANI)
and 927% (7.5 v/v% ANI), suggesting that the volume fraction
of ANI elevates the UTS as well as the εu of the hydrogels.
Further analysis of the stress−strain curves showed that the ANI
content improved the toughness but had a negligible effect on
the Young’s modulus of the hydrogels (Figure 2d). Additionally,
the microrheology characterization of the hydrogels with
different volume fractions of ANI displayed minor differences
in the storage and loss moduli (Figure S2), indicating that the
ANI has a minor effect on the viscoelastic properties of the DN
hydrogels. We speculated that the increase in the polyaniline
content comprised the strong interpenetration between the CS
and PAAm networks (Figure 2g). At the same time, owing to the
intrinsic strength of the PANI chains, the toughness and UTS of
the hydrogels slightly increased.
To examine the effect of CS, we compared the tensile
behaviors of the hydrogels with different contents of CS (Figure
2e). The UTS of 3, 5, and 7% CS DN hydrogels reached 2.07,
2.62, and 2.93 MPa, respectively, and the corresponding
ultimate tensile strain were 994, 927, and 848%, respectively.
Additionally, the elastic modulus and toughness of the DN
hydrogels increased with the fraction of CS increased (Figure
2f). It is worth pointing out that the presence of CS weakened
the UTS, although it benefited for rigidity. Microscopically, the
enhancement of the elastic modulus and toughness was
attributed to the reduction in the pore size, the increase in the
cross-linking density, and more hydrogen bonds associated with
the CS (Figure 2h).
Similar to other hydrogels, the conductive DN hydrogels were
able to dissipate a significant amount of mechanical energy,
leading to a large hysteresis during a loading−unloading cycle.
The hysteresis loop of the PANI/CS5-PAAm DN hydrogels
expanded gradually, with the increased ANI at the strain of 600%
(Figure 3a). Similarly, the hysteresis loop of the PANI7.5/CS-
PAAm DN hydrogels also broadened significantly with the CS
content at the strain of 600% (Figure 3c). All of these samples
displayed the mechanical hysteresis during the tensile test,
indicating that the CS and PANI doping served as the “sacrificial
bond” to dissipate the mechanical energy by dissociating the
ionic bond and hydrogen bond.43 Generally, the area of
hysteresis loops in the loading−unloading curves gives the
dissipated energy per unit volume, and the loops become more
evident with the increased strain. The dissipated energies per
unit volume (U) of PANI/CS5-PAAm DN hydrogels with
different ANI fractions were 1.67 MJ m−3 (2.5 v/v% ANI), 2.20
MJ m−3 (5 v/v% ANI), and 2.55 MJ m−3 (7.5 v/v% ANI), and
the corresponding dissipation coefficients (U coefficient) were
55.94, 63.40, and 65.19%, respectively (Figure 3b). Similarly, the
U and U coefficient of PANI7.5/CS-PAAm DN hydrogels grew
with the CS content (Figure 3d).
The dramatic improvement in the hysteresis and dissipation
coefficient was ascribed to the effective energy dissipation
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provided by the CS network in the DN hydrogels. Importantly,
the area of the hysteresis loop was positively correlated with the
tensile strain. As the strain increased, more dynamic cross-links
in the PANI/CS-PAAm DN hydrogel were destroyed to release
mechanical energy, leading to larger hysteresis loops (Figure
3e). The dissipated energy increased to 0.99 MJ m−3, and the
dissipation coefficient reached 52.94% at a strain of 500%
(Figure 3f). These results suggest that the covalent PAAm
network had a minor contribution to the energy consumption,
whereas the decross-linking of the CS networks and the
dissociation of the hydrogen bonds in the hydrogels played
the major role in energy dissipation.44
The decross-linking and dissociation were dynamic processes
that relied on both local and global deformations and occurred at
a certain time scale. We probed the upper bound of this
timescale by measuring the mechanical properties of the
hydrogels at different recovery times that were defined as the
time lag between the first and second loading−unloading cycles
(Figure S3). Compared to the mechanical behaviors of the first
loading−unloading cycle, the second loading−unloading cycle
with different recovery times displayed reduced Young’s
modulus and toughness. Interestingly, the mechanical properties
did not change anymore when the recovery time was longer than
5 min. These results suggest that some of the local structural
changes could not recover after the first loading−unloading
cycle, resulting in plastic deformation, and the characteristic
recovery time was less than 5 min.
In order to evaluate the cyclic stability of PCPD hydrogels in
long-term applications, we conducted 1000 continuous cyclic
tensile tests under 50% strain. The dynamics changes of stress
during loading−unloading cycles (Figure 3g) verify the excellent
fatigue resistance and long-term durability of the PCPD
hydrogel, which is of great importance for flexible sensors, soft
robots, and wearable devices.
The DN hydrogels could endure various deformations,
including stretching, twisted stretching, knotted stretching,
and cross-stretching, demonstrating their outstanding deform-
ability (Figure 3h). The excellent mechanical properties allowed
a piece of 20 × 10 × 1.46 mm3 DN hydrogel to readily sustain
the weight of a 2.18 kg object without noticeable cracks or
fractures (Figure S4).
To reveal the effect of ammonium sulfate on the micro-
structure, we measured the weight variation of the hydrogels
after being immersed in different ammonium sulfate solutions.
Compared to the composite hydrogel without ammonium
sulfate, the DN hydrogel soaked in the saturated ammonium
sulfate (43.47% (NH4)2SO4) solution had the lowest water
content (Figure S5), suggesting that the CS chains were heavily
cross-linked by ammonium sulfate to form the double-network
structure. As a result, the immersion of ammonium sulfate
increased the cross-linking density, leading to higher tensile
stress and elastic modulus.
The increased cross-linking density made the DN hydrogels
stiffer than the original ACPC hydrogel. The smaller pores
reduced the stress concentration and prevented crack expansion,
resulting in the toughening of the hydrogels. The CS network
and entangled PAAm network could decross-link and dissociate
to effectively consume energy during deformation, resulting in
an extremely high fracture energy of the PANI/CS-PAAm DN
hydrogels.
3.3. Antifreezing Properties. Usually, the water molecules
in hydrogels under subzero temperatures form ice particles, and
consequently, the hydrogels lose their softness, deformability,
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and toughness, vastly limiting their applications at low
temperature. Here, the incorporation of ammonium sulfate
into hydrogels can effectively increase the entropy of the
medium and lower the aggregation of water molecules. To
determine the range of the operating temperature, the
mechanical performances of the hydrogels at subzero temper-
atures were quantitatively measured using an electromechanical
universal testing machine equipped with an environmental
chamber. All the specimens were held in the chamber for 20 min
to achieve a thermal equilibrium before the test. The evolution
of the stress−stretch curves with decreasing temperature for the
0, 15, 30, and 43.47 (saturated) wt % (NH4)2SO4 gels are
plotted in Figure 4a−d and Figure S6. By comparison, we found
that the ultimate tensile strain increased with the (NH4)2SO4
concentration. The time lapse of the tensile test at subzero
temperatures is shown in Figure 4e and Movie S1. Based on the
trend of the stress−strain curves, we distinguished two types of
behaviors depending on the state of the gels: (i) regular hydrogel
behavior when the aqueous phase was in the liquid state; (ii)
slurry gel behavior when the aqueous phase was in the partially
frozen state that consists of a mixture of ice particles and salt
solution (illustrated by the insets of Figure 4f).45 These two
types of behaviors were separated by a critical temperature of
about −20 °C. As the temperatures decreased, the ultimate
tensile strain (Figure 4f) and the elastic modulus increased
slowly. Until the temperature reached below the critical value,
the gels began to become stiff and turned into slurry gels,
resulting in a sharp decrease in the ultimate tensile strain and a
sudden increase in the elastic modulus. This stiffening effect can
be attributed to the gradual increase in the volume fraction of ice
particles in the slurry gel. The ice particles were able to stiffen the
gel, while still allowing large deformation to occur through shear
yielding between them, similar to the toughening mechanism of
polymer nanocomposites.45 Additionally, the volume fraction of
ice particles also elevated the ultimate tensile stress of the DN
hydrogels (Figure S7).
To reveal the phase transition of (NH4)2SO4 and H2O in the
hydrogels at low temperatures, we characterized the transition
temperature of these chemicals using DSC (Figure S8). DSC
measurements show that the exothermic peak of frozen water in
the (NH4)2SO4 solutions was located at −18 °C (Figure S8a),
whereas the PANI/CS-PAAm DN hydrogels had an exothermic
peak at −20 °C (Figure S8b). The exothermic peaks are
expected to be associated with the freezing of water molecules.46
Particularly, the two distinct peaks of the DSC curves suggest
that the 0, 15, 30 wt % (NH4)2SO4 gels had not yet reached the
eutectic composition.
We propose that the abovementioned shift is the result of the
interactions of (NH4)2SO4 with the CS and polyacrylamide
polymer chains in the gel, and the equilibrium concentration of
(NH4)2SO4 inside the gel was lower than that in the aqueous
solution. On the one hand, the NH4+ and SO42− ions interfered
with the aggregation of water molecules and disrupted the
formation of ice particles, leading to a decreased freezing point
of the hydrogels (Figure 4f). On the other hand, the hydrophilic
amide and hydroxyl groups in the PAAm and CS networks also
contributed to the decrease in the freezing temperature by
forming hydrogen bonds between the polar groups and water
molecules. The combined effect of ions and polar groups
endowed the DN hydrogels with excellent low temperature
tolerance. Even when stored at −20 °C for 24 h, the PANI/CS-
PAAm hydrogels remained in an unfrozen state and were flexible
enough to withstand various deformations such as bending,
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ACS Applied Materials & Interfaces
twisting, stretching, and twisted stretching (Figure 4g and Figure
S9).
In addition to the good flexibility, the DN hydrogels
demonstrated remarkable toughness at low temperatures
(Figure S10). The toughness decreased dramatically with
increased temperature. Particularly, high toughness (∼33 MJ
m−3) was obtained at a temperature of about −40 °C for the
43.47% (NH4)2SO4 soaked DN hydrogel, suggesting that the
slurry phase significantly increased the toughness compared to
that of the regular gels under subzero temperatures.
Given the outstanding antifreezing performance, the DN
hydrogel may act as an antifreezing dress to protect the skin from
frostbite in cold weather. To confirm this speculation, we
designed a frostbite model on the back skin of rats. We placed
three liquid-nitrogen-frozen coins onto the bare skin, the
composite hydrogel-protected skin, and the DN hydrogel-
protected skin for 30 s (Figure 5a-c1). The composite hydrogel
turned brown after removing the cold coin (Figure 5b), implying
that the section of the composite hydrogel was converted into
the frozen state. As shown in Figure 5c2, a big white eschar
appeared on the unprotected skin, indicating the cold injury. By
comparison, no obvious eschar was observed on the skin
protected by the composite DN hydrogels. As for the
unprotected skin, almost all the cuticle was completely detached
from the epidermal layer, and many voids were generated in the
dermis during the frostbite (Figure 5di). In contrast, the skin
protected by the composite hydrogel showed slight damage with
fewer voids in the dermis (Figure 5dii), while the skin protected
by the DN hydrogel remained unscathed with complete
epidermis and dermis that had intact hair follicles and ordered
collagen fibers (Figure 5diii). These results suggest that the
antifreezing PANI/CS-PAAm DN hydrogel can be applied as
excellent protective dresses in a harsh environment.
3.4. Conductivity and Sensitive Sensing Performance
of the DN Hydrogels. The DN hydrogels have two conductive
mechanisms: one relies on the conductive chains of polyaniline,
and the other is through the excess ammonium sulfate that has
not been ionically cross-linked with CS. However, there was a
certain competition between these two conductive mechanisms.
As for polyaniline, the electrical conductivity of the hydrogel
increased from 3.94 to 4.83 S/m and decreased to 4.34 S/m as
the volume fraction of ANI varies from 2.5 to 7.5% (Figure 6a),
indicating that there is an optimal ANI concentration for the
conductivity. It is highly possible that the elevated ANI content
initially resulted in the increase in the polyaniline network
density, leading to an enhancement of the electrical con-
ductivity. However, further increase in the polyaniline network
density reduced the porosity and slowed down the transport of
the free ions, depressing the hydrogel conductivity. Similar effect
was also observed in the conductivity dependence on CS. As the
CS increased the density of the hydrogel network (Figure 2h),
the pore size gradually decreased and the electrical conductivity
decayed (Figure 6b).
To evaluate the potential of the PANI/CS-PAAm DN
hydrogels as strain sensors in harsh environments, we measured
the electrical conductivity of the hydrogels treated with different
(NH4)2SO4 solutions at different temperatures. The summar-
ized data are shown in Figure 6c. In addition to the outstanding
mechanical performance, the (NH4)2SO4-treated hydrogels
displayed excellent conductivity at −20 °C that is comparable
to that at RT.
Compared to other hydrogels, the PANI/CS-PAAm DN
hydrogels exhibited extremely high GF at a large strain, which
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makes them excellent candidates for strain sensors. The real-
time measurement of the relative resistance variation during the
stretching process is shown in Figure 6d. Usually, the GF is used
to evaluate the strain sensitivity of conductive hydrogels. As the
strain increased, the variation of the GF could be divided into I
(ε ≤ 100%) and II (100% < ε ≤ 600%) regions, where GFI was
2.046 and GFII was 3.915. By comparison, the sensitivity of the
PANI/CS-PAAm DN hydrogel is much higher than that of most
of the hydrogels reported in the literature.38,46−53 Generally, a
sensor needs good repeatability to ensure its reliability and
robustness. Hence, we measured the resistance change of the
DN hydrogels as strain sensors in small strain (10% ∼ 40%) and
relatively large strain (100% ∼ 400%) cycles (Figure 6e,f).
Indeed, the hydrogel sensors demonstrated good stability and
repeatability at different strains. We tested the resistance change
before and after 1000 cycles of continuous cyclic stretching
(tensile strain was fixed at 25%) (Figure S11). After 1000 cycles
of loading−unloading, the hydrogel could still function as a
sensor, which further demonstrates its fatigue resistance and
stability. To visualize the change in conductance in response to
the strain, a complete circuit connecting an LED bulb was
designed using the hydrogels as conductive wires. As the DN
hydrogel was stretched, the brightness of the LED bulb gradually
became dim because of the increased resistance (Figure 6g1−3).
To confirm the applicability, we attached the DN hydrogel-
based strain sensors to the human skin to detect diverse
macroscopic human activities. The changes in resistance upon
the mechanical stimulus were monitored in real time. The
relative resistance changes of the hydrogel strain sensor
corresponding to the different bending angles of the finger
(Figure 7a) at RT and −20 °C displayed good repeatability, as
shown in Figure 7b,c, respectively. In both cases, the outputs
increased monotonically with the bending angle (Figure 7d).
However, the magnitude of the resistance change at −20 °C was
smaller than that at RT for the same bending angle. The
repeatability for the resistance change also occurred in response
to the movement of the wrist (Figure 7e and Figure S12). In
addition to the large joint movements such as the finger and
wrist movements, subtle swallowing and facial expressions could
also be well captured using the hydrogel strain sensors (Figure
7f,g).
3.5. UV Radiation Resistance of the DN Hydrogels. The
PANI/CS-PAAm DN hydrogels with polyaniline doping
demonstrated an excellent UV resistance. As shown in Figure
S13, a commercially available UV sensor card was used to
measure the transparence of the hydrogels to UV light.
Compared to the composite hydrogels, the PANI/CS-PAAm
DN hydrogels greatly attenuated the UV signals. Additionally,
we measured the absorption spectra of hydrogels with different
contents of aniline using a UV−vis spectrometer. We
normalized the absorbance to the gel thickness to obtain the
absorption coefficient for different gels (Figure S14).
Quantitatively, the absorption coefficient increased with the
ANI content in the hydrogels, especially in the wavelength range
of 200−400 nm, suggesting strong UV resistance.
We summarized the quantitative data of the hydrogels in
Figure 8a−c to show the general trends of the mechanical and
electrical properties of the gels with increased concentrations of
ANI, CS, and (NH4)2SO4. For convenience, we normalized all
the properties to their maxima. The PANI/CS-PAAm DN
hydrogels displayed outstanding stretchability and conductivity
compared to other low-temperature hydrogels (Figure
8d).13,37,46,47,54,55 Importantly, its GF at large deformation
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ACS Applied Materials & Interfaces
exceeds that of other hydrogels reported in the literature (Figure
8e).2,7,46−53,56−73
Despite the outstanding performance of the conductive DN
hydrogels, there are a few limitations for their applications. First,
the volume fractions of the CS and ANI could only vary in a
narrow range, restricting the tunability of the hydrogels.
Additionally, the soaking of (NH4)2SO4 turned the hydrogels
into dark green, greatly reducing their transparency to visible
light. In the future, it is desirable to find another way to cross-link
the CS chains instead of using the (NH4)2SO4 solution such that
the usage of the hydrogels would be broadened.
4. CONCLUSIONS
In summary, we have prepared a set of ultra-tough, freezing-
tolerant, and conductive DN hydrogels. The excellent
mechanical properties of the PANI/CS-PAAm hydrogels were
achieved by the interpenetration between the dynamically cross-
linked CS network and the PAAM network. Further doping of
PANI and the soaking of the (NH4)2SO4 solution gave rise to
the outstanding electrical conductivity. The compound effect of
the mechanical and electrical properties allows the hydrogels to
gain supersensitivity for the strain, attaining a GF of 3.916 at
600% elongation. The hydrogel sensors not only displayed
remarkable performance at RT but also exhibited significant
reliability and stability at −20 °C, indicating its great potential
applications in harsh environments.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c08421.
FT-IR, microrheology, DSC, UV absorption, water
content and mechanical property measurements of the
hydrogels with different concentrations of CS and PANI,
different ammonium treatment, and thickness of the
hydrogel film with different aniline content on an acrylic
sheet (PDF)
Tensile test of hydrogel in an environment chamber at
−20 °C (MP4)
■
AUTHOR INFORMATION
Corresponding Author
Tianzhi Luo − CAS Key Laboratory of Mechanical Behavior
and Design of Materials, Department of Modern Mechanics,
University of Science and Technology of China, Hefei 230027,
China; orcid.org/0000-0003-2637-9605; Email: tzluo@
ustc.edu.cn
Authors
Jing Cong − CAS Key Laboratory of Mechanical Behavior and
Design of Materials, Department of Modern Mechanics,
University of Science and Technology of China, Hefei 230027,
China
Zhiwei Fan − South China Advanced Institute for Soft Matter
Science and Technology, South China University of
Technology, Guangzhou 510641, China
Shaoshan Pan − CAS Key Laboratory of Mechanical Behavior
and Design of Materials, Department of Modern Mechanics,
University of Science and Technology of China, Hefei 230027,
China
34951
www.acsami.org Research Article
Jie Tian − Experimental Center of Engineering and Materials
Sciences, University of Science and Technology of China, Hefei
230027, China
Weizhen Lian − South China Advanced Institute for Soft Matter
Science and Technology, South China University of
Technology, Guangzhou 510641, China
Shan Li − CAS Key Laboratory of Mechanical Behavior and
Design of Materials, Department of Modern Mechanics,
University of Science and Technology of China, Hefei 230027,
China
Sijie Wang − CAS Key Laboratory of Mechanical Behavior and
Design of Materials, Department of Modern Mechanics,
University of Science and Technology of China, Hefei 230027,
China
Dongchang Zheng − CAS Key Laboratory of Mechanical
Behavior and Design of Materials, Department of Modern
Mechanics, University of Science and Technology of China,
Hefei 230027, China
Chunguang Miao − CAS Key Laboratory of Mechanical
Behavior and Design of Materials, Department of Modern
Mechanics, University of Science and Technology of China,
Hefei 230027, China
Weiping Ding − CAS Key Laboratory of Mechanical Behavior
and Design of Materials, Department of Modern Mechanics,
University of Science and Technology of China, Hefei 230027,
China; orcid.org/0000-0002-3331-1011
Taolin Sun − South China Advanced Institute for Soft Matter
Science and Technology, South China University of
Technology, Guangzhou 510641, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c08421
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the National Science
Foundation of China (grant No. 11572316), the Fundamental
Research Funds for the Central Universities (grant No.
WK2480000006, WK2090050040), and the Science Project of
Anhui Province in China (grant No. 201903a07020019). We are
grateful for the technical support from Prof. Xinglong Gong.
This work was partially carried out at the Center for Micro and
Nanoscale Research and Fabrication at the University of Science
and Technology of China.
■
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