Supramolecular Materials 1 (2022) 100002

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Supramolecular Materials
journal homepage: http://www.keaipublishing.com/en/journals/supramolecular-materials/

Stimuli-responsive hydrogel sponge for ultrafast responsive actuator

Yukun Jian a,b,1, Baoyi Wu a,b,1, Xuxu Yang c, Yu Peng a,b, Dachuan Zhang a, Yang Yang d,
Huiyu Qiu a, Huanhuan Lu a,b, Jiawei Zhang a,b,∗, Tao Chen a,b,∗
a
Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Material
Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
b
School of Chemical Sciences, University of Chinese Academy of Sciences, 19A Yuquan Road, Beijing 100049, China
c
Department of Engineering Mechanics and Center for X-Mechanics, Zhejiang University, Hangzhou 310027, China
d
State Key Laboratory of Polymer Materials Engineering, College of Chemistry, Sichuan University, Chengdu 610064, China

a r t i c l e i n f o a b s t r a c t

Keywords: With the ability to deform in response to specific stimuli, polymeric hydrogel actuators are important bionic ma-
Hydrogel sponge terials. However, because shape deformation is derived from the diffusion of water molecules, the response rate
Stimuli-response of hydrogel actuators is usually slow, which severely limits their potential applications. In this work, a thermo-
Ultrafast
responsive PNIPAm hydrogel sponge is developed, and the hydrogel sponge shows ultrafast de-swelling/swelling
Actuator
capacity (equilibrium time 7 s) and large deformation degree (40%) due to the assistance of capillary force. Hy-
Grabbing living creatures
drogel sponge actuator with rapid response performance is further constructed, and the hydrogel sponge actuator
could be used to capture moving objects and living creatures. Moreover, light-controlled directional movement
can be achieved by incorporating photothermal functional components into the hydrogel sponge actuator. This
work would promote the application of hydrogel actuators in soft robots.

1. Introduction tial in the fields of biomedical and soft robots. However, like other
hydrogel-based actuators, the de-swelling or swelling of PNIPAm ac-
There are many fascinating biological activities in nature. Regardless tuator depends on the diffusion of water molecules, and the actuat-
of their size, they can move, grow and reproduce in different environ- ing speed is usually low (deswelling > 1 min, swelling > 20 min),[16]
ments. Inspired by nature, researchers are committed to imitating the which severely limits its practical applications, while humans and ani-
structure and function of animals or plants to design soft robots that are mals normally could complete the deformation action quickly (Fig. 1a).
as flexible and reliable as living creatures.[1] Hydrogel, as a novel intel- According to Fillmore’s theory, the diffusion rate of water in hydrogel
ligent material similar in the structure of biological tissues, with diverse is inversely proportional to the square of the hydrogel’s dimension.[23]
functions and strong compatibility, has been considered to be one of the However, though the microscopic hydrogel actuator possesses higher
best materials for designing soft intelligent robots.[2–6] Compared with response speed, the application in macroscopic field is limited.
other actuators such as liquid crystals and polymer films, hydrogel ac- As known, the thermo-responsive deswelling property of PNIPAm is
tuators could provide large deformation and better imitate the biology due to the transition from PNIPAm-water hydrogen bond to PNIPAm-
behavior of living organisms. Based on the stimuli-responsive property PNIPAm hydrogen bond. Therefore, there are two major strategies to
of hydrogels, and then using patterning and other methods to introduce promote the swelling/deswelling rate: (1) Increasing the contact area
anisotropic structure, researchers can construct hydrogel actuators that of the aqueous solution and the hydrogel, [24- 25] for instance, Agar-
can respond to a variety of external stimuli (such as temperature, humid- wal et al. have synthesized porous PNIPAm-based bilayer membranes
ity, pH, ions, etc.), which can be used in soft robots, artificial muscles, by electrospinning, and the PNIPAm polymer fibers greatly increase the
intelligent controllers and other fields.[7–15] specific surface area of the material, leading to the increasing of de-
Poly (N-isopropylacrylamid) (PNIPAm) hydrogel, as a typical formation speed.[25] (2) Increasing the size of pores in the hydrogel
thermal-induced shrinkage material, has been widely used to construct network, [26–29] which can help reducing the resistance encountered
hydrogel actuators.[16–22] With a LCST of 32 °C, close to human body during mass transport, thereby increasing the diffusion rate of solvents.
temperature, PNIPAm-based hydrogel actuators have promising poten- For example, Nie et al. have used pore-forming agent polyethylene gly-
col (PEG) to prepare composite hydrogel materials with large pores,

∗
Corresponding authors.
E-mail addresses: [email protected] (J. Zhang), [email protected] (T. Chen).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.supmat.2021.100002
Received 11 August 2021; Received in revised form 7 October 2021; Accepted 8 October 2021
2667-2405/© 2021 The Author(s). Published by Elsevier B.V. on behalf of KeAi Communications Co., Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Y. Jian, B. Wu, X. Yang et al. Supramolecular Materials 1 (2022) 100002

Fig. 1. (a) Schematic of a boy being able to grasp a moving ball. (b) Schematic of the deformation principle of the ultra-fast deformation actuator. (c) Schematic of
the water transport and thermal-induced deswelling principle of the PNIPAm sponge hydrogel. (d) Schematic of the synthesis strategy of PNIPAm sponge hydrogel.

which could shorten the deformation time required for ordinary hydro- solution environment, which indicates the application and development
gel materials from a few minutes to tens of seconds.[29] Besides, there direction of hydrogel-based soft robot with ultrafast actuating property.
are still some strategies to improve the porosity of hydrogels by adding
porogens (such as PEG, etc.) during the polymerization process[30–32]
or construct micro-scale units (such as microgels, polymer nanofibers or
2. Experimental section
polymer nanosheets, etc.).[33–35] Although, a few efficient strategies
have been implemented to improve the swelling/deswelling rate, the
2.1. Materials
swelling/deswelling rate is still not comparable to the living organisms
which could catch prey in seconds or catch the flying baseball. There-
N-Isopropyl acrylamide (NIPAm), acrylamide (AAm), sodium
fore, it is a great challenge to achieve ultrafast actuating rate in larger
alginate (Alg), polyvinyl alcohol (PVA), ammonium persulphate
sizes and change the dilemma where the existing hydrogel grippers usu-
(APS) were purchased from Shanghai Sinopharm Chemical
ally only grasp stationary objects.
Reagent Co., Ltd., N,N′-methylenebis (acrylamide) (BIS), N,N,N’,N’-
Herein, we have developed a hydrogel sponge actuator with ultrafast
tetramethylethylenediamine (TEMED), Fe3 O4 nanoparticles were
deformation rate that could grasp moving objects and living creatures
obtained from Aladdin Shanghai Reagent Co. Ltd.
(Fig. 1b, 1c). As shown in the Fig. 1d, ice, an environmentally friendly
and easy-to-remove porogen, is used to construct PNIPAm hydrogels
with large pores. In the presence of ice crystals, monomers are confined
to specific areas and polymerized in situ to form a locally aggregated 2.2. Instruments
polymer network, and hydrogel sponge with micropores that are filled
with water is obtained when the ice crystals melt. Due to the capil- The rheological measurements were performed on a Haake MARSIII
lary force caused by the ice-template method, the hydrogel sponge has rheometer equipped with a geometry of 25 mm parallel plates at 25°C.
fast thermo-responsive swelling/deswelling rate due to the presence of The tensile and compression tests were performed on a CMT-1104 uni-
capillary force. By adding a negative layer, a hydrogel sponge actuator versal testing machine (CMT-1104, SUST Electrical Equipment Co.). The
with ultrafast deformation capability is constructed and shows applica- dynamic mechanical analysis was performed on a DMAQ800 analyzer
tion prospects in the fields of moving-objects capture and life rescue. (DMAQ800, TA, America). The samples were frozen in liquid nitrogen
Besides, in the practical applications, it is hard and unrealistic to trans- for 10 min before lyophilizing with a freeze drier (FD-1C-50, Beijing
fer the hydrogel actuator to another solution with different temperature BoYiKang) at -35°C for about 48 h. The microscopic morphology was
in order to trigger the thermo-responsive actuating process. Therefore, observed using a field emission scanning electron microscope (SEM,
photothermal functional components are introduced into the hydrogel Phenon ProX) at an accelerating voltage of 10 kV. The internal pore
sponge actuator to accomplish light-controlled movement in the stable structure was characterized using a mercury porosimeter (AutoPore IV
9500).

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Y. Jian, B. Wu, X. Yang et al. Supramolecular Materials 1 (2022) 100002

Fig. 2. (a) Digital photos of the squeezing process of PNIPAm hydrogel sponge and ordinary PNIPAm hydrogel. (b) Comparison of de-swelling rates and appearance
of PNIPAm sponge hydrogel and ordinary PNIPAm hydrogel in warm water (40 °C). (c) Cyclic de-swelling and swelling performance of PNIPAm hydrogel sponge
as the temperature of the water varied between 20 °C and 40 °C. (d) De-swelling ratio of PNIPAm hydrogel sponge and Ordinary PNIPAm hydrogel at different
temperatures. (e) Comparison of de-swelling rate of PNIPAm hydrogel obtained by different synthesis strategies. [36–40] Scale bars: 1 cm.

2.3. Preparation of PNIPAm hydrogel sponge sheet. The polymerization system was placed in a 4 °C environment for
1 h.
NIPAm monomers (1.0 g), 10 mg of cross-linking agent Bis and 10
mg of free radical polymerization initiator APS were dissolved in 5 mL of 2.6. Actuation characterization
deionized water, shaken and ultrasonicated to obtain a clear and trans-
parent solution. After adding 10 𝜇L of TEMED to the solution, quickly The PNIPAm hydrogel sponge actuator and ordinary PNIPAm hydro-
poured the above solution into a self-made mold with a thickness of 1 gel actuator were cut into strips of 30 mm long, 3 mm wide, and 1 mm
mm, sealed the mold with a glass sheet, and placed it in a freezer at thick, respectively, and placed in warm water at 40 °C. The change in
-30 °C for 0.5 h. After the liquid was completely frozen, transfered the gel bending angle was recorded by using a camera.
mold to a refrigerator at a temperature of -5 °C and polymerized for 12
h. After the polymerization, the PNIPAm hydrogel sheet was soaked in 2.7. Finite element modeling
deionized water for 24 h to remove unreacted monomers.
The force condition of the hydorgel actuators during the actuating
2.4. Preparation of ordinary PNIPAm hydrogel process was analyzed and simulated by abaqus. The grid cell was con-
structed by C3D8RH:An 8-node linear brick, hybrid, constant pressure,
NIPAm monomers (1.0 g), 10 mg of cross-linking agent Bis and 10 reduced integration, hourglass control. And the modeling materials is
mg of free radical polymerization initiator APS were dissolved in 5 mL of Neo-Hookean.
deionized water, shaken and ultrasonicated to obtain a clear and trans-
parent solution. After adding 10 𝜇L of TEMED to the solution, quickly 3. Results and discussion
poured the above solution onto a glass sheet covered with pre-moistened
weighing paper, and sealed it with a 1 mm thick mold. Follow-up ex- At first, the basic properties of the hydrogel sponge and ordinary
periment steps are the same as above. hydrogel obtained using different synthetic strategies are characterized
to illustrate the difference in their structures. As shown in Figure S1a,
2.5. Preparation of bilayer PNIPAm hydrogel sponge actuator compared with the transparent ordinary PNIPAm hydrogel, the PNI-
PAm hydrogel sponge is almost completely opaque at room tempera-
APS (750 mg) was dissolved in 50 mL deionized water to obtain a ture. The light transmittance of them was quantitatively analyzed using
clear solution A. AAm monomer (1.4 g), crosslinker Bis (42 mg), Fe3 O4 an ultraviolet-visible spectrophotometer. The results are shown in Fig-
nanoparticles (200 mg) and TEMED (50 𝜇L) were dissolved in 20 mL ure S1b and Figure S1c. The transmittance of PNIPAm hydrogel sponge
of sodium alginate solution (2 wt%) to obtain solution B. An PNIPAm at room temperature is almost 0, while that of ordinary PNIPAm hy-
hydrogel sponge sheet with a size of 6 cm∗ 6 cm∗ 1 mm was soaked in 50 drogel reaches more than 95%. The difference in transparency of these
mL of solution A for 30 min, and placed in a mold with a thickness of two hydrogels is closely related to the difference in the distribution of
2 mm. Solution B was poured on the gel sheet and sealed with a glass polymer networks. Specifically, in the frozen state, the squeezing effect

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Y. Jian, B. Wu, X. Yang et al. Supramolecular Materials 1 (2022) 100002

Fig. 3. (a) SEM images of the microstructure of PNIPAm hydrogel sponge and ordinary PNIPAm hydrogel. (b) Quantitative measurement of the pore structure of the
PNIPAm hydrogel sponge and ordinary PNIPAm hydrogel by a mercury porosimeter. (c) Schematic of the preparation of fluorescent hydrogels synthesized by two
different methods. (d) Fluorescence emission spectra of the fluorescent hydrogels synthesized by two different methods. (e) The structural model and the explanation
of the rapid de-swelling mechanism of PNIPAm hydrogel sponge. Scale bars: 1 cm.

of ice crystals prevents the polymer from being evenly distributed, and Because of the presence of water filled micro pores, water molecules
the uneven structure usually results in an opaque appearance. After the could quickly release from or fill the pores of the PNIPAm hydrogel
polymerization reaction is completed, these squeezed polymer chains sponge with the assistance of capillary force, the de-swelling/swelling
are fixed due to permanent chemical cross-linking. Moreover, PNIPAm rate of the PNIPAm hydrogel sponge is significantly enhanced. There-
hydrogel sponge remained opaque after being placed at 20 °C water fore, when the two samples of PNIPAm hydrogel sponge and ordinary
for a long time after synthesis, indicating that the white appearance hydrogel were alternative immersed in 40 and 20 °C baths, respectively.
was not caused by the LCST effect of PNIPAm. Additionally, the water The de-swelling rate and de-swelling ratio of the two hydrogels are sig-
in the PNIPAm hydrogel sponge would flow out when being pressed, nificantly different. Fig. 2b depicts the time-dependent de-swelling be-
while no water was seen if the ordinary PNIPAm was pressed (Fig. 2a, havior of PNIPAm hydrogel sponge and ordinary PNIPAm hydrogel. The
Movie S1). The results indicate water molecules was immobilized by PNIPAm hydrogel sponge exhibits a very fast de-swelling rate: the sam-
the PNIPAm polymer networks in the ordinary PNIPAm hydrogel, while ple reaches an equilibrium state within 7 seconds, and the de-swelling
micro channels that was filled with free water molecules presented in ratio at this time is about 0.4. Although the ordinary PNIPAm sample
the PNIPAm hydrogel sponge due to the inefficient hydrogen bonding quickly become opaque in 40 °C warm water, its volume does not change
between water molecules and PNIPAm chains in the frozen state. The significantly after 1 minute. Fig. 2c shows that the swelling rate of hy-
difference in the mechanical properties of the two hydrogel samples also drogel sponge is equivalent to the de-swelling rate, and the de-swelling
provides evidence for this hypothesis. The results in Figure S2 show that rate of PNIPAm hydrogel sponge remains stable during the several de-
the maximum tensile stress of PNIPAm hydrogel sponge is only half that swelling/swelling cycles, indicating that its micro porous structure has
of ordinary PNIPAm hydrogel. not been damaged in the process of cycling.

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Y. Jian, B. Wu, X. Yang et al. Supramolecular Materials 1 (2022) 100002

Fig. 4. (a) Schematic of the structure and bending mechanism of actuator based on PNIPAm hydrogel sponge. (b) Bending rates of actuators based on PNIPAm
hydrogel sponge and ordinary PNIPAm hydrogel. (c) The ultrafast actuator based on PNIPAm hydrogel is used to grab a moving ball in water. (d) Application
demonstration of ultrafast actuator based on PNIPAm hydrogel sponge: emergency rescuer. Scale bars: 1 cm.

Not only the de-swelling and swelling speed of PNIPAm hydrogel depicts the scanning electron microscopy (SEM) images of the two kinds
sponge is significantly faster than that of ordinary PNIPAm hydrogel, of PNIPAM hydrogels. It is found that the ordinary PNIPAm sample ex-
the de-swelling ratio of PNIPAm hydrogel sponge is also much smaller hibits uniform and closed pores, and the distribution is between 1-10
than that of ordinary PNIPAm hydrogel at different temperatures. As μm. Simultaneously, the PNIPAm sponge sample shows open pore struc-
shown in Fig. 2d, below 30 °C, both hydrogel samples hardly de-swell. ture with large and interpenetrating pores, it has uneven distribution
When the temperature reaches 35 °C, the volume of PNIPAm hydrogel and the pore size can be up to 100 μm. The difference in structure is re-
sponge decreases rapidly, shrinking to about 40% of the initial volume, lated to the polymerization method. For the PNIPAm hydrogel sponge,
and the de-swelling of ordinary PNIPAm hydrogel is still not obvious. it is frozen before polymerization, and the water in the hydrogel precur-
When the temperature further increased, the de-swelling ratio of PNI- sor froze to form large-sized ice crystals, which occupy the position of
PAm hydrogel sponge decreased slightly with the increase of tempera- NIPAm monomers. The polymerization reaction of polymer monomers
ture. For ordinary PNIPAm hydrogels, no precipitous reduction in vol- is carried out in a confined space. After the polymerization reaction is
ume can be observed. Utilizing the difference in de-swelling ratio of the completed, the melting of ice crystals makes the spatial confinement
two hydrogel samples, we can “splice” the two hydrogels together to from the outside disappear. However, the chemical crosslinks formed
construct a composite hydrogel. Although the chemical components of between the molecular chains act as new spatial confinements, making
the two parts are exactly the same, they will produce different deforma- the molecular chains unable to move freely.
tions at the same temperature, leading to complex deformations of the Furthermore, mercury porosimeter was used to quantitatively ana-
entire sample and the experimental results are shown in Figure S3. The lyze the pore structure of the two hydrogels. The experimental results
de-swelling and swelling rates were calculated by dividing the volume in Fig. 3b show that the pore size of the ordinary PNIPAm hydrogel is
change rates by the swollen hydrogel volume, and compared with some significantly smaller than that of the PNIPAm hydrogel sponge, which
representative literatures that report fast shrinking PNIPAm hydrogels. is consistent with our SEM observations above. In addition, it can be
The results in Fig. 2e show that the PNIPAm hydrogel sponge in this concluded that the pore volume in PNIPAm hydrogel sponge accounts
work has excellent performance in both de-swelling rate and swelling for 92% of the total volume, which is much larger than 77% pore vol-
rate. Lyophilizing tests were conducted on the fully swollen samples to ume of Ordinary PNIPAm hydrogel. The results indicate that the poly-
calculate their solid contents, and the results are shown in Figure S4, mer network in PNIPAm hydrogel sponge can only exist in a small area
after freeze-drying, there is no significant difference in the remaining due to the confinement effect of ice crystals. Correspondingly, in the
proportions of the two gels, indicating that the difference in de-swelling area where the polymer exists, the concentration of PNIPAm polymer
performance between the two hydrogels are mainly caused by structural will be much higher than the average concentration of Ordinary PNI-
differences. PAm hydrogel. This conclusion can also be proved by indirect evidence.
In order to further analyze the influence of hydrogel structure on DAEAN,[41] a monomer with aggregation-induced luminescence effect
performance, direct and indirect methods were used to characterize the (AIE) was copolymerized into the PNIPAm network by different synthe-
microstructure of hydrogels synthesized by different strategies. Fig. 3a sis strategies (Fig. 3c). The results in Fig. 3d show that when the concen-

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Y. Jian, B. Wu, X. Yang et al. Supramolecular Materials 1 (2022) 100002

Fig. 5. (a) Calculation of heat transfer in the bilayer hydrogel. (b) Calculation results and experimental photos of local deformation of the bilayer hydrogel under
local NIR light. (c) Light-controlled two-dimensional directional movement of a six-arm snow-like hydrogel on a plane. (d) The movement trajectory of the snowflake
gel under the control of NIR light. Inset picture: The irradiation position and movement direction of the bilayer snowflake gel. Scale bars: 1 cm.

tration of the fluorescent components are exactly the same, the fluores- ing to the required deformation procedure, but also the deformation
cence intensity of P (NIPAm-co-DAEAN) fluorescent hydrogel sponge needs to be completed in a short time. The rapid shrinkage properties of
is more than twice that of ordinary P (NIPAm-co-DAEAN) fluorescent the PNIPAm hydrogel sponge encourages us to construct actuator with
hydrogel, which can confirm our hypothesis on the hydrogel structure. ultrafast deformation performance. Combining it with a temperature-
According to the above experimental results, it can be concluded that insensitive pan paper, a paper-based actuator is obtained. As shown in
the hydrogel sponge structure synthesized by the ice template method Fig. 4a, when the hydrogel actuator is placed in warm water, the volume
has a great promotion effect on the de-swelling/swelling process of the of the PNIPAm hydrogel sponge is reduced, while the volume of the pan
hydrogel. This promotion effect is related to two structural characteris- paper does not change, causing the entire system to bend toward the
tics of the hydrogel sponge: the polymer aggregation effect caused by hydrogel sponge side. Due to the rapid de-swelling of PNIPAm hydrogel
the confinement of ice crystal extrusion and the capillary effect on mass sponge, the bending speed of the entire actuator is also very fast. PNI-
transfer of large-size open pores (Fig. 3e). First, compared with ordi- PAm hydrogel sponge and ordinary PNIPAm hydrogel were used to con-
nary PNIPAm hydrogel network with evenly distributed crosslinking struct paper-based hydrogel actuators, respectively. Fig. 4b depicts the
points, the polymer network of PNIPAm hydrogel sponge is restricted time-dependent bending behavior of paper-based actuators constructed
to a smaller area, forming a large number of polymer clusters. Thus, by two different hydrogels. When placed in 40°C warm water, the PNI-
most of the water molecules are captured in the three-dimensional net- PAm hydrogel sponge actuator bends rapidly and reaches the final equi-
works via hydrogen bond with PNIPAm chains in ordinary PNIPAm hy- librium state within 10 s and the maximum bending angle is about 400°.
drogel, while most of the water molecules (∼70 %) are free distributed For ordinary PNIPAm hydrogel actuator, it takes 5 min to get the maxi-
in the PNIPAm hydrogel sponge via capillary aisles. When thermally mum bending angle of about 400°. Calculated based on the time required
stimulated, the polymer clusters are less restricted and can therefore to reach the maximum deformation state, the deformation speed of the
shrink quickly, in contrast, the ordinary PNIPAm hydrogel network is PNIPAm sponge-based actuator can reach more than 30 times that of
restricted by the tension of chemically crosslinking points and is diffi- ordinary PNIPAm hydrogel.
cult to produce significant deformation. Secondly, the capillary action The extremely fast deformation speed of PNIPAm hydrogel sponge
would encourage the PNIPAm hydrogel sponge to squeeze out and ab- actuator enables it to finish some tasks that ordinary hydrogel actua-
sorb water molecules quickly, leading to the rapid de-swelling/swelling tor cannot do, such as capturing moving objects. Fig. 4c demonstrate
of the PNIPAm hydrogel sponge. the ability of the rapid-bending actuator to grab a moving ball: a small
In some specific conditions, such as rescue, capture, and transporta- black ball moves along the bottom of a container filled with warm wa-
tion, not only the soft actuator is required to be able to deform accord- ter at a uniform speed of 4 cm/s. When it reaches a certain position,

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the grabber quickly enters the water and catches the ball. The gripping (Fig. 5d, Movie S4). Therefore, the light-controlled movement on a two-
action can be completed within several seconds and then it rises from dimensional smooth substrate can be realized, which has expanded the
the water. The rescue of live crabs perfectly demonstrates the two major freedom of motion of hydrogel actuator.
characteristics of our actuator: soft and rapid-deformation. As shown in
Fig. 4d, a crab accidentally falls into warm water (36°C). Because crabs 4. Conclusions
are a kind of cold-blooded animals, the temperature of experimental
condition is fatal to them, it is urgent to rescue it from the high temper- In this work, PNIPAm hydrogel sponge with interconnected pore
ature environment in a short time. The PNIPAm hydrogel sponge based structures have been fabricated. Compared with PNIPAm hydrogel that
rapid actuator was made as "emergency rescuers". As shown in Fig. 4d, it is prepared by conventional method, the PNIPAm hydrogel sponge
needs only 7 seconds to grab the crab and lift it from the dangerous area. shows large porosity and polymer aggregation due to the extrusion of
It is worth mentioning that our grabber can lift the crab from the warm ice crystal, leading to ultrafast thermally induced de-swelling/swelling
water and stay in the air for several seconds, which proves the excellent properties with a de-swelling ratio of 0.4. Moreover, a bilayer hydro-
gripping ability of our actuator. After transferring the crab to cold water, gel sponge actuator with rapid deformation-recovery ability have been
the grabber quickly opens and the crab is released. It can be clearly ob- developed, and the deformation could be completed within 10 s, which
served from the picture in Fig. 4d that the crabs in the cold water are still exhibits a 30 folds enhancement in actuating speed, and the ultrafast
alive, which proves that our rescue operation is successfully completed. hydrogel sponge actuator could be used to grasp moving creatures. In
The rescue of multiple crabs can prove the reusability of the gripper. As addition, by introducing photothermal functional components and de-
shown in Figure S5 and movie S2, within 40 seconds, the thermally in- signing the shape of the hydrogel sponge, light-controlled directional
duced rapid deformation actuator completed 3 bending-recovery cycles, movement can be realized. We believe our strategy could promote the
and rescued 3 crabs from the warm water, all of the crabs survived. This development of soft robots with practical applications.
application provides feasible solutions for soft rescue robots and motion
robots. Conflict of interest
Additionally, the de-swelling/swelling rates can be tuned by intro-
ducing other polymers, such as polyvinyl alcohol (PVA) and sodium al- The authors declare no competing financial interest.
ginate (Alg) into PNIPAm hydrogel sponge (Figure S6a). Figure S6c-d
depicts the time-dependent de-swelling behavior of PNIPAm hydrogel Acknowledgments
sponge with PVA or Alg, and the experimental results show that both
PVA and Alg could reduce the de-swelling rate of the PNIPAm hydrogel This work was supported by National Key Research and Develop-
sponge. The possible theoretical explanation is shown in Figure S6b, the ment Program of China [2018YFB1105100], National Natural Science
macromolecular chains and the PNIPAm polymer network are entangled Foundation of China [51873223, 52073295], Key Research Program of
with each other, which hinders the movement of the polymer network Frontier Science, Chinese Academy of Sciences [QYZDB-SSW-SLH036].
during the thermal shrinkage of the PNIPAm network, moreover, the hy-
drophilic polymer chains could form interactions with water molecules, Supplementary materials
which could slow down the elimination of water molecules. In Figure
S7, A series of ultrafast hydrogel actuators with different bending rates Supplementary material associated with this article can be found, in
were constructed and combined to realize the multi-level deformation the online version, at doi:10.1016/j.supmat.2021.100002.
demonstration. When placed in warm water at 40°C, the three different
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