We investigated the mechanical properties of corn starch (CS)/poly(vinyl alcohol) (PVA)/borax hydrogels reinforced by clay platelets, silica (SiO2) nanospheres, or cellulose nanofibers (CNFs). The effects of these reinforcing agents on the tensile properties of the hydrogels were quite different; the fracture stress of SiO2/CS/PVA/borax composite hydrogels increased with SiO2 concentration, whereas that of clay/CS/PVA/borax composite hydrogels was high at a low clay concentration but low at high clay concentrations; for CNF/CS/PVA/borax composite hydrogels, although the elastic modulus was highly enhanced by adding CNF, the fracture stress was very low because of the stress relaxation during the elongation. This result came from differences in the dispersibility of each filler and the reinforcing ability. These composite hydrogels were constructed by multi-crosslinking, such as hydrogen bonding between CS and PVA, CS and PVA crystals, complexation between borate and PVA (partly CS), and the crosslinking between each filler and polymer. The self-healing ability of SiO2 and clay composite hydrogels was examined. As a result, the SiO2/CS/PVA/borax composite hydrogels possessed an excellent self-healing ability, whereas the clay/CS/PVA/borax composite hydrogels had a poor self-healing ability.
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