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. 2024 Mar 10;17(6):1275.
doi: 10.3390/ma17061275.

Facile Synthesis of Dual-Network Polymer Hydrogels with Anti-Freezing, Highly Conductive, and Self-Healing Properties

Affiliations

Facile Synthesis of Dual-Network Polymer Hydrogels with Anti-Freezing, Highly Conductive, and Self-Healing Properties

Yuchen Jin et al. Materials (Basel). .

Abstract

We report the synthesis of poly(acrylamide-co-acrylic acid)/sodium carboxy methyl cellulose (PAMAA/CMC-Na) hydrogels, and subsequent fabrication of dual-network polymer hydrogels (PAMAA/CMC-Na/Fe) using as-prepared via the salt solution (FeCl3) immersion method. The created dual-network polymer hydrogels exhibit anti-swelling properties, frost resistance, high conductivity, and good mechanical performance. The hydrogel swells sightly when immersed in solution (pH = 2~11). With the increase in nAA:nAM, the modulus of elasticity experiences a rise from 1.1 to 1.6 MPa, while the toughness undergoes an increase from 0.18 to 0.24 MJ/m3. Furthermore, the presence of a high concentration of CMC-Na also contributes to the enhancement of mechanical strength in the resulting hydrogels, ascribing to enhanced physical network of the hydrogels. The minimum freezing point reaches -21.8 °C when the CMC-Na concentration is 2.5%, owing to the dissipated hydrogen bonds by the coordination of Fe3+ with carboxyl (-COO-) in CMC-Na and PAMAA. It is found that the conductivity of the PAMAA/CMC-Na/Fe hydrogels gradually decreased from 2.62 to 0.6 S/m as the concentration of CMC-Na rises. The obtained results indicates that the dual-network hydrogels with high mechanical properties, anti-swelling properties, frost resistance, and electrical conductivity can be a competitive substance used in the production of bendable sensors and biosensors.

Keywords: conductivity; dual-network hydrogels; frost resistance; self-healing; swelling resistance.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
(a) Schematic representation depicting the synthesis procedure of PAMAA/CMC-Na/Fe hydrogels. (b) Cross-linking of -COO with Fe3+ in the hybrid hydrogels.
Figure 2
Figure 2
(a) Water content of PAMAA/CMC-Na and soaking PAMAA/CMC-Na/Fe; Effects of different (b) nAA:nAM, (c) CMC-Na concentration, (d) Fe3+ concentration, and (e) different soaking time on water content.
Figure 3
Figure 3
The stability and swelling of hydrogels after soaking in PBS solution (pH = 7.4) for 24 h: (a) physical state, (b) swelling ratio, and (c) equilibrium water content of PAMAA/CMC-Na and PAMAA/CMC-Na/Fe hydrogels.
Figure 4
Figure 4
Effects of different nAA:nAM on (a) swelling ratio and (e) equilibrium water content of the PAMAA/CMC-Na/Fe hydrogels. Effects of different CMC-Na concentrations on (b) swelling ratio and (f) equilibrium water content of the PAMAA/CMC-Na/Fe hydrogels. Effects of different Fe3+ concentrations on (c) swelling ratio and (g) equilibrium water content of the PAMAA/CMC-Na/Fe hydrogels. Effects of different soaking time on (d) swelling ratio and (h) equilibrium water content of the PAMAA/CMC-Na/Fe hydrogels.
Figure 5
Figure 5
Properties of PAMAA/CMC-Na/Fe hydrogels after soaking in solution of different pH: (a) physical state, (b) swelling ratio (12 h), (c) swelling ratio (30 days), and (d) equilibrium water content.
Figure 6
Figure 6
(ac) The effects of different nAA:nAM on (a) strain, (b) elastic modulus, and (c) toughness of the hydrogels. (df) The effects of different CMC-Na concentration on (d) strain, (e) elastic modulus, and (f) toughness of the hydrogels. (gi) The effects of different soaking time on (g) strain, (h) elastic modulus, and (i) toughness of the hydrogels.
Figure 7
Figure 7
(a) DSC curves of hydrogels. Effects of (c) different nAA:nAM and (e) CMC-Na concentration and (g) Fe3+ concentration and (i) Fe3+ soaking time on anti-freezing performance of the hydrogels. (b) Freezing point, and the effects of (d) different nAA:nAM and (f) CMC-Na concentration and (h) Fe3+ concentration and (j) Fe3+ soaking time on the freezing point.
Figure 8
Figure 8
The flexibility performance of (a) P(AM-co-AA)/CMC-Na hydrogels, (b) P(AM-co-AA)/CMC-Na/Fe3+ hydrogels, and (c) P(AM-co-AA)/CMC-Na/Fe3+/NaCl hydrogels at room temperature and −20 °C.
Figure 9
Figure 9
Conductivity testes of PAMAA/CMC-Na/Fe hydrogels: (a) Simplified depiction of the movement of ions within the hydrogels. (b) The bulb brightness and (c) schematic drawing of the hydrogels under different strains: (B1) 0, (B2) 50%, and (B3) 100%. (d) The bulb brightness and (e) schematic drawing of hydrogels under different states: (D1) initial, (D2) cutting, (D3) electrical healing. Effect of different (f) nAA:nAM and (g) CMC-Na concentration and (h) Fe3+ concentration and (i) Fe3+ soaking time on the conductivity of hydrogels.

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