Carbohydrate Polymers 231 (2020) 115736

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Carbohydrate Polymers
journal homepage: [Link]/locate/carbpol

Continuous liquid interface production of alginate/polyacrylamide T

A R T I C LE I N FO A B S T R A C T

Keywords: A recently developed three-dimensional (3D) gel-printing technology, namely continuous liquid interface pro-
Continuous liquid interface production duction (CLIP), was utilized to fabricate supramolecular shape memory hydrogels with high resolutions and
Hydrogel complex 3D geometries. The UV-curable ink for CLIP was composed of hydrogel precursors (alginate and ac-
Toughness rylamide) and a photo-initiator (ammonium persulfate). As expected, the double network formed from ionically
Conductivity
crosslinked alginate and covalently crosslinked polyacrylamide endowed the printed hydrogels with excellent
Supramolecular shape memory
mechanical properties. Meanwhile, due to the reversible metal-ligand coordination interaction, the hydrogel
could be temporarily immobilized into an optional shape after introducing calcium ions and return to its original
shapes upon ion removal, exhibiting ion-triggered shape memory effect. Moreover, the presence of ions greatly
improved the conductivity of the resultant hydrogels. Such 3D printed versatile hydrogels with complex geo-
metries demonstrated the potential for selected applications, particularly in load-bearing materials and flexible
electronic devices.

1. Introduction et al., 2017; Zhao, Zhang et al., 2017; Meng et al., 2014). For example,
Tang et al. designed a triple supramolecular SM hydrogel utilizing the
As a water-rich stimuli-responsive material (Bilici & Okay, 2013; supramolecular interaction between Ca2+ and alginate, a thiol–di-
Dai et al., 2015; Gulyuz & Okay, 2014; Li, Dunn, Zhang, Deng, & Qi, sulfide interchange reaction, and the hydrogen-bonding effect (Tang,
2017; Xu et al., 2015), shape memory (SM) hydrogels have the cap- Wen, Xu, Pi, & Wen, 2018). Such supramolecular SM hydrogels are well
ability to stabilize a temporary shape and then return to their perma- suited for more complicated applications like drug carriers to achieve
nent geometry in response to external stimuli such as heat, light and sequential release of various payloads.
chemicals (Inomata et al., 2012; Miyamae, Nakahata, Takashima, & In spite of those impressive successes, further development of SM
Harada, 2015; Si et al., 2017; Torbati & Mather, 2016; Zhao, Huang, hydrogels has been largely hampered by their simple geometries the
Wang, Sun, & Tong, 2017; Zhao, Zhang, Liu, Zhou, & Liu, 2017). In conventional manufacturing methods can only produce (Odent et al.,
recent years, SM hydrogels have experienced impressive progress of SM 2017). For example, in tissue engineering, a precise and complex 3D
hydrogels in the field of biomedical and smart materials (Hu, Guo, structure of a hydrogel scaffold is particularly desired. Consequently,
Kahn, Aleman‐Garcia, & Willner, 2016; Zhao, Huang et al., 2017; Zhao, more and more researchers attempted to fabricate complex-structured
Zhang et al., 2017). Thermo-responsive SM hydrogels triggered by heat hydrogels with various 3D printing technologies, such as direct ink
are mostly investigated. However, they often encounter obstacles when writing (DIW), stereolithography apparatus (SLA) and digital light
applied under ambient conditions where heat sources are not easily processing (DLP) (Huang et al., 2017; Pawar et al., 2016; Yuk & Zhao,
available, such as soft robotics, textile and biomedical area (Lu, Le, 2018). For instance, Li et al. obtained novel double network hydrogels
Zhang, Huang, & Chen, 2017). To address this issue, supramolecular SM with different geometries via DIW from sodium alginate, acrylamide
hydrogels commonly based on supramolecular interactions and dy- and acrylic acid (Li et al., 2017). Martinez et al. employed SLA to
namic covalent bonds have been introduced thanks to their multi-sti- fabricate drug-loaded hydrogels (Martinez, Goyanes, Basit, & Gaisford,
muli sensitivity and recyclability at room temperature (Zhao, Huang 2017). Zhang et al. utilized DLP to print biostructures and tissues from

⁎
Corresponding authors at: State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute at Sichuan University, Chengdu, 610065, China.
E-mail addresses: weizhang@[Link] (W. Zhang), canhuilu@[Link] (C. Lu).

[Link]
Received 2 October 2019; Received in revised form 22 November 2019; Accepted 11 December 2019
Available online 20 December 2019
0144-8617/ © 2019 Elsevier Ltd. All rights reserved.
B. Huang, et al. Carbohydrate Polymers 231 (2020) 115736

Fig. 1. Schematic of a CLIP printer and its working mechanism.

the acrylamide ink (Zhang et al., 2018). Nonetheless, the layer-by-layer tetramethylethylenediamine (TEMED) were supplied by Sigma-Aldrich
processing of DIW induces obvious staircasing effect on the prints, (Shanghai, China). All the regents and ingredients were used without
leading to the low resolution of the resultant 3D structures (Hong et al., further purification. Distilled water was used throughout the experi-
2015). Whereas SLA and DLP are also layer-by-layer printing processes, ment.
which are not continuous and can hardly achieve a high print speed and
excellent print accuracy synchronously. Fortunately, an innovative 2.2. Preparation of the ink for CLIP
stereolithography 3D printing technology, namely continuous liquid
interface production (CLIP), was developed in 2015, which well over- Sodium alginate (0.36 g, 2 wt%), AAm (2.89 g, 0.04 mol), 7.32 mg
come these shortcomings in traditional 3D printing (Tumbleston et al., TEMED (0.15 mol%, molar ratio of TEMED/AAm), MBA (1.40 mol%,
2015). As demonstrated in Fig. 1, the CLIP printer is able to transform molar ratio of MBA/AAm) were dissolved in deionized water (18 g).
the 2D model files into 3D entity structures when the UV-curable liquid Then, ammonium persulfate (0.09 mol%, molar ratio of AP/AAm) was
resin is illuminated by patterned UV radiation. On the principle of added to initiate the radical photo-polymerization of AAm monomers
oxygen-inhibited photopolymerization to create a dead zone under UV exposure. In order to improve the resolution of the prints,
throughout the printing process, CLIP allows layerless and monolithic crystal violet and methylene blue were incorporated to minimize the
fabrication, resulting in the prints with superb resolution at a rather UV-light scattering.
high printing speed. Specifically, it took less than 10 min to create a
layerless 3D part with a height of 5 cm (Tumbleston et al., 2015). 2.3. CLIP 3D printing
Alginate/polyacrylamide hydrogels have been widely investigated
owing to their excellent mechanical properties and biocompatibility, The printing models were designed using the 3D MAX software and
and so on (Bahrami, Akbari, & Eftekhari-Sis, 2019; Morelle et al., 2018). exported as STL files. The printing process was conducted on the CLIP
And alginate/acrylamide hydrogels with arbitrary shapes and compli- 3D printer (Laichuang 3D Science & Technology Co. Ltd, Chengdu,
cated structures may find a wide range of applications. Herein, the CLIP China) equipped with an oxygen-permeable window (60 × 70 mm2)
technology was employed for the first time to fabricate supramolecular and a UV-laser of 405 nm. The working mechanism for this printer can
SM alginate/polyacylamide hydrogels with various geometries. It is be found in the literature (Tumbleston et al., 2015). The exposure time
worth to note that the currently available inks for CLIP are almost oil- for each layer (10 μm) was set to 0.1 s with a light power density of
based ones (Janusziewicz, Tumbleston, Quintanilla, Mecham, & 10 mW/cm2
DeSimone, 2018) making the 3D prints not suitable for many advanced
applications, such as biomedical and tissue engineering. The prints 3. Characterization
were subsequently immersed in a calcium chloride solution to introduce
ionic crosslinking. The resultant two interpenetrating polymers inside 3.1. Rheological properties
the hydrogel with both ionic and covalent crosslinking created strong
inter-molecular interactions, giving rise to its excellent mechanical Rheological measurements on the printing ink were performed with
properties. The highest compressive strength reached 547.2 kPa when a rheometer (AR2000ex, TA Instruments Ltd., Crawley, UK) on the
the compressive strain was 75 %, and the hydrogel could still maintain steady-shear-rate scanning mode at room temperature. A circular par-
its integrity even at 90 % compressive strain. Moreover, due to the allel plate (diameter = 35 mm) with a gap of 0.5 mm was used.
supramolecular interactions between the calcium ions and the car-
boxyls on sodium alginate, the shape of the hydrogel could be tempo-
3.2. FTIR analysis
rally fixed when immersed in a calcium chloride solution in 30 s. And it
could return to its original shape after the removal of calcium ions. In
The chemical structures of the samples (alginate, polyacrylamide
addition, the existence of a large amount of movable metal ions pro-
and CLIP-printed hydrogel with ionic crosslinking) were examined by a
vided the hydrogel with prominent ionic conductivity, which was also
Fourier transform infrared (FTIR) spectrometer (Nicolet Magna-IR 550,
highly stress-sensitive.
USA) in the wavenumber range from 600 to 4000 cm−1 with a re-
solution of 2 cm-1. For the printed hydrogel sample with ionic cross-
2. Experimental section linking, it was freeze-dried until the mass remained unchanged and
then ground into fine powder for FTIR analysis.
2.1. Materials
3.3. Micro-morphology and pore structure characterization
Sodium alginate, calcium chloride, methylene blue, and ammonium
persulfate (AP) were all purchased from Kelong Chemicals Reagent The printed hydrogel was freeze-dried for 24 h before the SEM ob-
Company (Chengdu, China). Acrylamide (AAm), N, N′-Methylenebis servation. The obtained samples were coated with gold for 60 s using a
(acrylamide) (MBA), crystal violet, N, N, N′, N′- vacuum sputter coater (Quorum Q150 T ES, UK) and then observed

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B. Huang, et al. Carbohydrate Polymers 231 (2020) 115736

with SEM (LEO 1530, Germany) at 10 kV. The specific surface area and early studies (Sun et al., 2017) they can also serve as the photo-initiator
the pore structure of the freeze-dried hydrogel were determined from and the crosslinking accelerator for polyacrylamide, respectively. The
nitrogen adsorption-desorption experiments at −196 °C using an ac- UV radiation is able to break down the peroxy bond of AP to generate
celerated surface area and porosimetry system (NOVA-2000E, more free radicals. In this sense, UV can promote the polymerization of
Quantachrome, USA). AAm, making the gelation speed compatible with the 3D printing speed
(during CLIP 3D printing, the exposure time for each slice was only
3.4. Mechanical properties 0.1 s). Moreover, the photo absorbers of crystal violet and methylene
blue were added to absorb excess refracted light, thereby inhibiting
For tensile testing, the samples were fabricated by replica-molding photo-polymerization of the resin outside the projection area. Note that
from cuboids (width = 15 mm, thickness = 4 mm and gauge the photo absorber was one of the key ingredients to ensure high
length = 50 mm), while column shaped molds (diameter = 25 mm, printing resolution (Zhang et al., 2018). The as-prepared ink was rather
height = 15 mm) were used to produce samples for compressive flowable at ambient conditions and exhibited a stable viscosity (η) of
testing. Photo-polymerization of the hydrogel was completed after ex- around 970 mPa•s at a shear rate ranged from 0.01 to 10 s−1 (see Fig.
posure to the UV light of the CLIP printer for 3 h. All the samples were S1a and b, and the discussion in the Supporting Information).
then soaked in a calcium chloride solution (0.5 wt%) for 4 h to stabilize Subsequently, the CLIP 3D printer was employed to run the printing
the physicochemical properties of the hydrogels. The mechanical of alginate-polyacrylamide hydrogel (see Video S1 in the Supporting
properties were measured on a universal testing machine (Instron 5567, Information). During CLIP 3D printing, a computer-aided design (CAD)
USA) in ambient conditions. For both compressive and tensile tests, the file made from the 3D MAX software was sliced into two-dimensional
crosshead speed was set at 2 mm/min. renderings with 10 μm for each slice and the exposure time of each
layer was set to 0.1 s. The patterned UV projection from the CLIP
3.5. Swelling ratio measurements printer triggered the photopolymerization of the flowable aqueous ink
in a defined area to solidify into a hydrogel by opening the double
To test the swelling ratio before and after ionic crosslinking, sam- bonds on AAm and MBA (covalent crosslinker) to form polyacrylamide
ples were put into an oven at 70 °C until the weight remained un- with a covalently crosslinked network structure (Fig. 2b). Due to the
changed and then soaked in deionized water for a specified time until existence of oxygen entering from the oxygen-permeable window, there
the equilibrium was attained. The sample weight was measured every was an uncured area (dead zone) between the window and the cured
few hours. The swelling ratio of the hydrogel was calculated as follows: part (see Fig. 1), which ensured a continuous printing process, leading
to a high printing speed as well as an amazing apparent resolution of
Wt − Wo
Swelling ratio = the product. Consequently, a series of hydrogels with complex struc-
Wo
tures, such as gear, star and letters (Fig. 2f–h), were successfully fab-
where Wt is the sample weight after swelling and Wo is the dry weight. ricated. Note that the hydrogel samples might appear in various colors,
owing to the different dyes used and/or soaking times in the solution.
3.6. Shape memory effect Next, the 3D printed hydrogel with a covalent crosslinking structure
was immersed in a calcium chloride solution to ionically crosslink its
To evaluate the shape memory properties, the hydrogel sample was alginate part (Fig. 2c). And the soaking time was optimized to 4 h (see
re-shaped under external force in 0.5 wt% calcium chloride solution to Fig. S2 and the discussion in the Supporting Information).
fix the temporary geometry. Subsequently, the hydrogel sample was
soaked in 0.1 M EDTA•2Na solution to recover its original shape.
4.2. FTIR analysis
3.7. Ionic conductivity measurements
The FTIR spectra were depicted in Fig. 3. There were a broad peak
The changes of ionic conductivity for the hydrogels under various near 3400 cm−1 for OeH stretching, two sharp peaks at 1620 and
compressive strains were detected using a multimeter (UNI-T 61E, 1410 cm−1 for asymmetric and symmetric COOe stretching, a peak at
China) and a universal testing machine (Instron 5567, USA) at a com- 1320 cm−1 for C–H deformation with secondary alcohols, and three
pressive speed of 2 mm/min. The testing circuit was consisted of a cy- peaks at 1120, 1090, and 1030 cm−1 for asymmetric CeOeC
lindrical hydrogel (diameter = 25 mm, height = 15 mm), conductive stretching, CeO stretching in CHeOH, and CeO stretching in CeOeC
copper wire and the multimeter. structures in the spectrum of alginate. For polyacrylamide, the spec-
trum showed two peaks at 3410 and 3200 cm−1 representing the
4. Results and discussion stretching vibration of NeH, and a sharp peak at 1670 cm−1 for C]O
stretching. There were also bands at 1620 cm−1 (NeH for primary
4.1. CLIP 3D printing of the alginate-polyacrylamide hydrogels amine), 1450 cm−1 (CH2 in-plane scissoring), 1420 cm−1 (CeN for
primary amide), 1350 cm−1 (C–H), and 1120 cm−1 (NH2 in-plane
The formulation of the liquid resin and the detailed photo-poly- rocking). In the spectrum of ion-crosslinked hydrogel, the characteristic
merization process for CLIP 3D printing were provided in Fig. 2a–f. The peaks of both alginate and polyacrylamide could be observed. However,
UV-curable ink was composed of water, sodium alginate, AAm the intensity of the bands related to OeH (3400 cm−1), primary amide
monomer and other functional additives (photoinitiator, covalent (1620 and 1420 cm−1), CeO in CHeOH structure (1090 cm−1), sym-
crosslinker, and dye). And Fig. 2a showed the chemical structures of the metric CeO stretching in CeOeC structure (1030 cm−1) decreased.
main ingredients of the ink. Two crosslinkable polymers, poly- Notably, compared with alginate, the wavenumber for asymmetric
acrylamide and sodium alginate, were selected as the main components −COO- stretching of alginate in the ion-crosslinked alginate/poly-
of the hydrogels. And MBA and calcium chloride were used as covalent acrylamide hydrogel decreased, while that for symmetric −COO-
and ionic crosslinkers for polyacrylamide and sodium alginate, re- stretching increased. These results consistently revealed the interaction
spectively. The photo-polymerization of AAm was triggered by AP between calcium ions and the carboxyl groups on sodium alginate ac-
under UV irradiation. The optimum photoinitiator concentration was at cording to the literature (Nakamoto, 2006). Hence, it could be con-
0.09 % (molar ratio of AP/AAm) as demonstrated in Fig. S1c in the cluded that the hydrogel with assumed structure in Fig. 2 had been
Supporting Information. Note that AP and TEMED are widely used as successfully prepared.
the redox initiator pair for polymerization. However, according to some

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B. Huang, et al. Carbohydrate Polymers 231 (2020) 115736

Fig. 2. (a)–(e) Scheme of the chemical composition of liquid resin and the mechanism of photo-polymerization and crosslinking; (f)–(h) 3D printed gear, star and
letters.

4.3. Morphologies and pore structures of CLIP printed hydrogel concentrations (0.2 wt%, 0.5 wt% and 0.8 wt%) were measured to be
0.519 ± 0.107, 0.052 ± 0.009 and 0.035 ± 0.011 mm, respectively
SEM was employed to intuitively observe the micro morphologies of (the pores were randomly selected from the SEM images for size mea-
the 3D printed hydrogel ionically crosslinked with different content of surement). Obviously, the pore size of hydrogels decreased when
Ca2+. From the SEM images in Fig. 4, the average pore sizes for hy- soaked in a calcium ion solution with a higher concentration. Moreover,
drogels ionically crosslinked in CaCl2 solutions with different the BET tests also suggested a similar trend in pore size as well as the

Fig. 3. FTIR spectra of alginate, polyacrylamide (a), and 3D printed alginate/polyacrylamide hydrogels after ionic crosslinking (b).

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B. Huang, et al. Carbohydrate Polymers 231 (2020) 115736

Fig. 4. SEM images of 3D printed hydrogels ionically crosslinked in CaCl2 solutions with different concentrations (0.2 wt% (a), 0.5 wt% (b) and 0.8 wt% (c)).

specific surface area upon ion concentration changes (see Table S1 and 4.5. Mechanical properties
Fig. S3 in the Supplementary Information for details). This is normal
because a higher crosslinking density will induce a smaller pore size of Both tensile and compressive mechanical properties of the hydro-
the hydrogel (Zhang, Zhang, Lu, & Deng, 2012). Notably, the existence gels were examined, and the results were presented in Fig. 6a and b.
of abundant interconnected pores could endow the hydrogel with a The ionic crosslinking with calcium ions greatly improved the hydro-
large specific surface area and provide a medium for the transport of gels’ tensile strength (60.8 ± 1.7 kPa) and elongation at break
functional species (such as conductive ions, nutrients and wastes). (508.3 ± 21.8 %), corresponded to the enhancement of 396.8 % in
strength and 229.1 % in elongation as compared with those without ion
4.4. Effect of ionic crosslinking on the swelling behaviors of hydrogels cross-linking. In the meantime, the compressive strength of the hy-
drogel was also significantly increased after ionic crosslinking (from
Hydrogels are a kind of water-rich materials with 3D network 156.4 ± 17.6 to 468.7 ± 97.6 kPa at a compressive strain of 75 %).
structures. Hydrogel will swell and its volume will expand when soaked The improvement of mechanical properties should be possibly attrib-
in water. The infiltration of water into a polymer matrix results in the uted to the following reasons. First, the unzipping of ionic crosslinks
weakening of intermolecular force and the increase of molecular dis- facilitated energy dissipation. Second, the long molecular chains of
tance. However, the volume expansion is always accompanied by the polyacrylamide with covalent crosslinks were favorable for the main-
contraction of the hydrogel network structure. When such two opposing tenance of hydrogels’ structural integrity when their ionic crosslinks
trends become balanced, a swelling equilibrium state is reached. were damaged by external stress.
Thereby, the swelling behaviors are important features of hydrogels In order to further explore the anti-fatigue and anti-compression
highly associated with their internal structures. Generally, the equili- properties of hydrogels, a compression recovery test (five cycles, 2 mm/
brium swelling ratio is governed by the chemical composition as well as s) was performed on the samples both with and without ionic cross-
the crosslinking density of hydrogel. linking. For the sample without ionic crosslinking, the five compression
Herein, the effect of ionic crosslinking on the swelling ratio of de- curves overlapped almost completely (Fig. 6c). And the dissipation
hydrated hydrogel in deionized water was measured, and the results energy corresponding to the cyclic compression curve also had little
were illustrated in Fig. 5. The hydrogels had been ionically crosslinked difference (around 7278.9 J/m3). It indicated that the mechanical in-
in calcium chloride solutions with different concentrations. All the tegrity of hydrogel was well maintained after five compressive cycles.
hydrogels swelled right after immersed in water. And the water ab- In contrast, for the ionically crosslinked hydrogel, its compression
sorption rate obviously decreased as the Ca2+ concentration of the strength was greatly improved. Except for the larger area of the first
soaking solution increased. After 170 h, the hydrogels reached their hysteresis loop, the later four test curves almost coincided (Fig. 6d).
equilibrium swelling ratios of 18.3 ± 0.1 (without ionic crosslinking), And the dissipation energy of ion-crosslinked hydrogel was distinctly
13.0 ± 0.6 (0.2 wt%), 10.7 ± 0.1 (0.5 wt%) and 9.2 ± 0.3 (0.8 wt higher than that of the sample without ionic crosslinking (Fig. 6e and f).
%), respectively. The decreased equilibrium swelling ratio for the hy- Fig. 6g intuitively demonstrated the anti-compression performance of a
drogels ionically crosslinked in a higher concentration Ca2+ solution CLIP printed cylindrical hydrogel subjected to 90 % compressive de-
agreed well with their higher crosslinking density that restricted more formation on a universal testing machine. The hydrogel was not cru-
extensively the molecular chain extension during swelling. shed and could restore to the original shape rapidly when the pressure

Fig. 5. (a) The swelling ratios of hydrogels ionically crosslinked in calcium chloride solutions with different concentrations at different swelling time; (b) The
equilibrium swelling ratios for different hydrogel samples.

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B. Huang, et al. Carbohydrate Polymers 231 (2020) 115736

Fig. 6. Tensile (a) and compressive (b) stress-strain curves for hydrogels with and without ionic crosslinking. Cyclic compressive stress-strain curves for hydrogels
without (c) and with (d) ionic crosslinking at a maximum strain of 75 % for 5 compression-release cycles, respectively. Histograms of hysteresis energy corresponding
to cyclic compressive stress-strain curves of hydrogels without (e) and with (f) ionic crosslinking. (g) A cylindrical hydrogel sample subjected to a compressive strain
of 90 % could return to its original shape after the release of external force.

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B. Huang, et al. Carbohydrate Polymers 231 (2020) 115736

was released, suggesting its excellent anti-fatigue and anti-compression shown in Fig. 7c, the triangular hydrogel could be fixed into a torch-like
properties. shape with Ca2+ crosslinking (time = 0 h). And when soaked in ED-
TA•2Na, the hydrogel took 6 ± 1 h to gradually return to its initial
state. Furthermore, the recovered hydrogel was subjected to the second
4.6. Shape memory effect shape memory test. It could still be fixed into a temporary torch-like
shape and recover the initial shape after EDTA treatment, suggesting its
Sodium alginate is a natural polysaccharide extracted from sea- excellent cyclability in SM.
weed, whose molecule chains are formed by β-D-mannuronate (M)
blocks and α-L-guluronate (G) blocks. Various metal ions can form
temporary supramolecular interactions with carboxyl groups on the 4.7. Ionic conductivity
molecular chain of G blocks due to the high inclusiveness of the in-
teraction. Also, the supramolecular interaction is highly responsive to Owing to the presence of abundant metal ions and the porous
external stimuli such as pH changes and the exclusion of metal ions, structures, the hydrogels could be used as a conductive material. To
which endows the alginate hydrogel with fantastic shape memory ef- visually demonstrate the ionic conductivity of the hydrogel, a complete
fect. To evaluate the ion-triggered shape memory effect, a strip-shaped circuit was designed, which consisted of a cylindrical hydrogel, a blue
hydrogel sample was deformed into various shapes (such as helix and U light-emitting diode (LED) and a dry battery. As shown in Fig. 8a and b,
shapes) by external force, and then soaked in 0.1 M CaCl2 or FeCl3 the LED was lighted up when the circuit was switched on. In addition,
solution. As expected, the sample could ‘memorize’ its temporary shape when the hydrogel was compressed, the brightness of the LED was re-
very rapidly (∼30 s) as a result of strong supramolecular interactions markably increased, suggesting its potential applications in pressure
between sodium alginate and metal ions (see Fig. 1). Afterward, by sensors. Moreover, Fig. 8c quantitatively showed the resistance (R) of
using EDTA•2Na which has a much higher chelating constant, the metal different hydrogels as a function of compressive strain (from 0 to 50 %).
ions could be removed from the hydrogel. And ultimately it recovered Obviously, the R value would decrease under compression and the
its initial strip shape at room temperature (Fig. 7a and b). The shape hydrogel with a higher metal ion concentration exhibited lower R at the
memory properties were also verified on a triangle-shaped hydrogel. As same compressive strain.

Fig. 7. (a, b) Shape memory effect of the hydrogel induced by metal ions (calcium and iron ions); (c) Photographs that demonstrated the shape recovery process of
the 3D-printed hydrogel in EDTA and the second SM behavior of hydrogel.

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B. Huang, et al. Carbohydrate Polymers 231 (2020) 115736

Fig. 8. (a, b) Photographs and corresponding schematics that visually demonstrate the electrical conductivity changes of hydrogels under compression; (c) the R for
hydrogels fabricated at different metal ion concentrations as a function of compressive strain.

5. Conclusion Hong, S., Sycks, D., Chan, H. F., Lin, S., Lopez, G. P., Guilak, F., et al. (2015). 3D printing of
highly stretchable and tough hydrogels into complex, cellularized structures. Advanced
Materials, 27(27), 4035–4040.
In this work, we report a mechanically strong and ionically con- Hu, Y., Guo, W., Kahn, J. S., Aleman‐Garcia, M. A., & Willner, I. (2016). A shape-memory DNA-
ductive 3D double network hydrogel of alginate/polyacrylamide with based hydrogel exhibiting two internal memories. Angewandte Chemie International Edition,
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fascinating supramolecular SM properties, which was 3D printed for the Huang, L., Jiang, R., Wu, J., Song, J., Bai, H., Li, B., et al. (2017). Ultrafast digital printing
first time by the novel CLIP technology. This technology allowed a toward 4D shape changing materials. Advanced Materials, 29(7), 1605390.
rapid and continuous production of complex 3D structured hydrogels Inomata, K., Terahama, T., Sekoguchi, R., Ito, T., Sugimoto, H., & Nakanishi, E. (2012). Shape
memory properties of polypeptide hydrogels having hydrophobic alkyl side chains.
without sacrificing their resolution and fidelity. Moreover, due to the Polymer, 53(15), 3281–3286.
chelation of carboxyl groups of sodium alginate with metal ions, the Janusziewicz, R., Tumbleston, J. R., Quintanilla, A. L., Mecham, S. J., & DeSimone, J. M.
(2018). Layerless fabrication with continuous liquid interface production. PNAS, 113(42),
hydrogel could fix a temporary shape in a short period of time in metal
11703–11708.
ion solutions, and recover its original shape after metal ion removal. Li, V. C. F., Dunn, C. K., Zhang, Z., Deng, Y., & Qi, H. J. (2017). Direct ink write (DIW) 3D
Given that the hydrogel was highly compressible/stretchable and had a printed cellulose nanocrystal aerogel structures. Scientific Reports, 7(1), 8018.
Lu, W., Le, X., Zhang, J., Huang, Y., & Chen, T. (2017). Supramolecular shape memory hy-
high content of water to host movable ions, it exhibited a prominent drogels: A new bridge between stimuli-responsive polymers and supramolecular chemistry.
ionic conductivity which was sensitive to external forces. It was en- Chemical Society Reviews, 46(5), 1284–1294.
visaged that these CLIP printed hydrogels with complex 3D geometries Martinez, P., Goyanes, A., Basit, A., & Gaisford, S. (2017). Fabrication of drug-loaded hydrogels
with stereolithographic 3D printing. International Journal of Pharmaceutics, 532, 313–317.
and attractive properties would play important roles in various ad- Meng, H., Xiao, P., Gu, J., Wen, X., Xu, J., Zhao, C., et al. (2014). Self-healable macro-/mi-
vanced applications, such as in load-bearing materials and flexible croscopic shape memory hydrogels based on supramolecular interactions. Chemical
Communications, 50(82), 12277–12280.
electronic devices. Miyamae, K., Nakahata, M., Takashima, Y., & Harada, A. (2015). Self-healing, ex-
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Author contribution drogel through host–guest interactions. Angewandte Chemie International Edition, 54(31),
8984–8987.
Morelle, X., Illeperuma, W., Tian, K., Bai, R., Suo, Z., & Vlassak, J. (2018). Highly stretchable
Bingxue Huang finished completed the literature writing and ana- and tough hydrogels below water freezing temperature. Advanced Materials, 30(35),
1801541.
lyzed experimental results.
Nakamoto, K. (2006). Infrared and Raman spectra of inorganic and coordination compounds.
Rui Hu and Zhouhang Xue completed the picture production in this Handbook of vibrational spectroscopy.
paper together. Odent, J., Wallin, T. J., Pan, W., Kruemplestaedter, K., Shepherd, R. F., & Giannelis, E. P.
(2017). Highly elastic, transparent, and conductive 3D-printed ionic composite hydrogels.
Jiangqi Zhao, Tian Xia and Qingye Li carried out experiments. Advanced Functional Materials, 27(33), 1701807.
Wei Zhang and Canhui Lu conceived and designed the experiments. Pawar, A. A., Saada, G., Cooperstein, I., Larush, L., Jackman, J., Tabaei, S., et al. (2016). High-
performance 3D printing of hydrogels by water-dispersible photoinitiator nanoparticles.
Science Advances, 2(4), e1501381.
Acknowledgements Si, Y., Wang, L., Wang, X., Tang, N., Yu, J., & Ding, B. (2017). Ultrahigh-water-content, su-
perelastic, and shape-memory nanofiber-assembled hydrogels exhibiting pressure-re-
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This work was supported by the National Natural Science
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