Chitosan composite hydrogels reinforced with natural clay nanotubes

Here, chitosan composites hydrogels were prepared by addition of halloysite nanotubes (HNTs) in the chitosan KOH/LiOH/urea solution. The raw chitosan and chitosan/HNTs composite hydrogels were obtained by heat treatment at 60°C for 8h and then regeneration in ethanol solution. The viscosity of the composite solution is increased with HNTs content. The Fourier transform infrared spectroscopy (FT-IR) shows that the hydrogen bonds interactions exist between the HNTs and the chitosan. X-ray diffraction (XRD) results show that the crystal structure of HNT is not changed in the composite hydrogels. The compressive property test and storage modulus determination show that the mechanical properties and anti-deformation ability of the composite hydrogel significantly increase owing to the reinforcing effect of HNTs. The composites hydrogel with 66.7% HNTs can undergo 7 times compression cycles without breaking with compressive strength of 0.71MPa at 70% deformation, while pure chitosan hydrogel is broken after bearing 5 compression cycles with compressive strength of 0.14MPa and a maximum deformation of 59%. A porous structure with pore size of 100-500μm is found in the composite hydrogels by scanning electron microscopy (SEM), and the pore size and the swelling ratio in NaCl solution decrease by the addition of HNTs and the immersing of ethanol. Chitosan/HNTs composite hydrogels show low cytotoxicity towards MC3T3-E1 cells. Also, the composite hydrogels show a maximum drug entrapment efficiency of 45.7% for doxorubicin (DOX) which is much higher than that of pure chitosan hydrogel (27.5%). All the results illustrate that the chitosan/HNTs composite hydrogels show promising applications as biomaterials.